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Chemistry 303
fall, 2002
SECOND EXAMINATION
7:30 PM, NOVEMBER 11th, 2002
Duration: 2.5 hr
Name____________________________________________________________
Lab TA__________________________________________________________
(if you do not know his/her name, give day of lab section. NOT Hooley nor Kim)
This is an "open book" examination; you may use anything which is not alive.
Note: if you do not know the complete or specific answer, give a partial or general answer-WRITE SOMETHING
Write only in the space provided for each question.
Score:
I_________ /12
II_________ /28
III_________ /17
IV________ /26
V.________./19 The second part is tough...
Total:

/100

There are 10 pages in this exam, and a separate Data Sheets section. All 13C NMR spectra are "protondecoupled", as usual. Please check now to be sure you have a complete set.
If you are using a resonance argument in your answer, draw the relevant resonance structures.
Be aware that in Problem I you may "purchase" the unknown structure (I) for a multi-point penalty. Go to the
front and request the structure of the proctor, and he will deduct the appropriate points.
Please be aware that a small number of students will be taking the exam at different times up until the afternoon on
Tuesday. It would be well not to discuss the exam until after that time.

PLEDGE:_________________________________________________________________

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I. 12 pts). Consider the structure of compound Z. On the chart below, please draw your best
prediction for the 1H NMR spectrum. Take into account chemical shift positions, splitting patterns, and label each
set of peaks with the #H giving rise to it. Use the additivity table to back up your chemical shifts where
appropriate; show your calculations. Label and explain coupling patterns. Specify approximate J values.
Step 1. Draw in all the individual hydrogens on the
structure, and label each hydrogen or group of equivalent
hydrogens: A, B, C, etc.

Cl

Step 2. Calculate the chemical shifts wherever

possible. Specify the approx. chemical shifts
for Hs where you cannot calculate them directly.
Step 3. Predict the pattern of peaks for each group of equivalent
protons, assuming pure 1st order spectra.

Br
Z

CN

Step 4. Draw the spectrum, and indicate on your spectrum the

relative #Hs responsible for each peak or set of peaks.

intensity

300 MHz

[end exam]
II. (26 pts) Consider the spectral data for Structure I on the Data Sheets.

0 ppm

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A. (4 pts) From the 4000-1500 cm-1 region of the infrared spectrum alone, which of the following functional
groups are ruled out? (circle those which are ruled out, and explain in one sentence how you came to that
conclusion.):
carbonyl group (C=O) _______________________________________________________________________
alcohol (-OH)______________________________________________________________________________
amino (-NH2)______________________________________________________________________________
cyano (-CN)________________________________________________________________________________
aldehyde (RCHO)___________________________________________________________________________
ether (R-O-R)______________________________________________________________________________
monosubstituted alkyne (R-CCH)______________________________________________________________
B. (2 pts).
1. From the mass spectral data, what is the molecular weight of the compound? ______

2. Give an estimate of the number of carbon atoms. 3 4

9 (circle one)

C. (6 pts) From the 1H NMR spectrum, for each set of equivalent protons, give the chemical shift, the relative
area, and describe the splitting pattern (singlet, doublet, triplet, quartet, quintet, sextet, etc) including approximate
coupling constants. You should estimate the J values as best you can.
Chemical Shift Rel. Area

Splitting pattern

Approx. J

1.

_________________________________________________________________________________

2.

_________________________________________________________________________________

3.

_________________________________________________________________________________

4.

_________________________________________________________________________________

5.

_________________________________________________________________________________

6.

_________________________________________________________________________________

7.

_________________________________________________________________________________
continued

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E. (2 pt) How many non-equivalent carbon atoms are indicated in the 13C NMR spectrum? _______
F. 1. (8 pts) Draw the structure for I which best fits all the data (review your IR conclusions). Explain in
detail how your structure fits the pattern of peaks (splitting) in the 1H NMR spectrum. Label the groups of
equivalent H in your structure for reference. You need not show calculation of chemical shift positions, but you
might do this to confirm your structure. You can buy structure I (6 pt penalty).

2. (2 pts) Specify which carbon in your structure gives the peak at 171 ppm in the 13C NMR
spectrum.

3. (2 pts) Explain how your structure fits the IR spectrum, based on the peaks from 4000-1500 cm-1.

4. (2 pts) Explain how your structure is consistent with the parent ion region of the mass spectrum.

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III. (17 pts) Consider the three isomers, M, N, and P.
Assume you do not have access to comparison spectra from authentic samples. Imagine you have one set of
spectra in front of you which is from one of the following.
H3CO

OCH3
H

H
M

H3CO

H
OCH3

H3CO

H
H

H3CO

A. (4 pts) Could one distinguish N from P using the 1H NMR alone? Explain.

B. (4 pts) Could one distinguish N from P using only the 1500-4000 cm-1 region of the IR? Explain.

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contdinued

H3CO

OCH3
H

H
M

H3CO

H
OCH3

H
N

H3CO

H
H

H3CO
P

C. (3 pts) Could one distinguish M from P using 13C NMR with broad band decoupling (the usual)? Explain.

D. (3 pts) Could one distinguish M from N using 13C NMR with broad band decoupling? Explain.

E. (3 pts) Could one distinguish M from N using the parent ion region of the mass spectra? Explain

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IV. (26 pts) Henry is a closet philatelist and, in the course of that activity, recently ran into
an interesting chemical problem. Some stamps can be identified by their "watermark" and this can be visualized by
dipping the stamp into a "Phlatelic Watermark Fluid". It is described on the bottle as a "hydrochlorofluorocarbon"
but no more information is given. He enlisted the help of the master NMR spectroscopist, R. Hooley, and some
spectra were collected. Consider the spectra in the Data Sheets for Structure II, pages 5-7. From the boiling
point and other hints, the candidate structures seem to be A-C. Fluorine has an effect on chemical shift like that of
Cl, but it has spin 1/2 and J values a similar to H (Data Sheets: p 8, Table 3).
H

Cl

H
C
H

Cl

C
A

Cl

C
F
Cl

H
C

C
B

Cl

F
Cl

C
C

A. Considering the pattern of the peaks and the chemical shifts in the 1H NMR spectrum,
1. (5 pts) Is structure A fully consistent with the spectrum? If not, explain what you expect for A.

2. (5 pts) Is structure B fully consistent with the spectrum? If not, explain what you expect for B.

3. (5 pts) Is structure C fully consistent with the spectrum? If not, explain what you expect for C.

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B. (4 pts) It is hoped that you found one and only one structure consistent with the 1H NMR data. If
not, please write a generic answer to this part. If so, please explain how that structure is also consistent with the
pattern of the 19F NMR spectrum (do not concern yourself with the chemical shift). I. e., what coupling gives rise
to this 19F NMR spectrum?

C. (4 pts) In the same way, explain how that structure is consistent with the pattern of the 13C NMR
spectrum. I. e., what couplings gives rise to this 13C NMR spectrum?

D. (3 pts) Draw any one of the possible staggered conformations of C using a Newman projection.
Choose the proper template and fill it in.

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V. ( 19 pts) Consider the molecules F-K and the selected IR peaks listed for the C=O stretch. Note that
there is a change in the frequency as a phenyl group replaces a methyl, and a change when Cl atoms replace H.
Note also that in I and J, there are two peaks in this region, of different relative intensity.
O
H3C

O
CH3

F
-1

1720 cm

CCl3

CH3
G
1692 cm-1

O
CH2Cl

1718 cm-1

-1

1692 cm (larger)
1716 cm-1 (smaller)

CHCl2
J
-1

1692 cm (smaller)
1716 cm-1 (larger)

A. ( 5 pts) Rationalize the difference in position of the peak for F ("normal") and in G (shifted). It always
helps to express you answer with structures.

B. (5 pts) Rationalize the difference in position of the peak for G compared to the peak for H.

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continued

C. (7 pts) Things are not always so simple. You might need to refine your thinking about the effect of the
CCl3 group with this analysis, and go beyond the ideas presented in lecture. Rationalize the observation of two
peaks from I and J compared to one from H.
Hint #1:
It might be helpful to analyze the conformations
of the compounds. The most favored conformation type
is shown here (X = H or other substituent) both in the Newman
projection and the sawhorse projection. The alternative, with a
group eclipsed with the Ph substituent, is an energy maximum
as one rotates the front carbon due to repulsion.
Hint #2.
IR spectroscopy is a "fast" camera, unlike NMR, and the
spectrum can show peaks for separate entities which are rapidly
interconverting.

O
X

O rotation
X
Ph

X
Ph

favored, energy minimum

O
X

O
X
Ph

X
Ph
X
disfavored, energy max.
In your discussion, you should explain clearly: (a) why there are two peaks and
(b) why each is at the particular position observed.
For 2 pts bonus credit, you can explain why the relative intensity of the two peaks changes between I and J.

D. (2 pts). Would you expect the approx. barrier to rotation for the bond between CH3 and C=O in G to be:
0.01 kcal/mol

2 kcal/mol

20 kcal/mol

100 kcal/mol ?

(circle single best answer; explain ambiguity, if any)

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