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Chemistry 303
fall, 2000
SECOND EXAMINATION
7:30 PM, NOVEMBER 13th, 2000
Duration: 2.0 hr
Name____________________________________________________________
Lab TA__________________________________________________________
(if you do not know his/her name, give day of lab section. NOT Hooley nor Chlenov)
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__________/28
II__________/36
III_________ /22
IV_________ /14

Total:

/100

There are 9 pages in this exam, followed by five pages of spectra. All 13C NMR spectra are "proton-decoupled",
as usual. Please check now to be sure you have a complete set. You may detach the Data Sheets for your
convenience, but remember to re-staple the rest of the exam securely when you hand it in.
If you are using a resonance argument in your answer, draw the relevant resonance structures.
Be aware that in Problem I and II, you may "purchase" the unknown structure (X, A) for a 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:_________________________________________________________________

I. (28 pts) Consider the spectral data for molecule X on p 11/12.

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)______________________________________________________________
disubstituted alkyne (e.g., Me-CC-Me)_________________________________________________________
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. 4

9 (circle one)

C. (6 pts) For each set of equivalent protons, give the 1H NMR 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.

_________________________________________________________________________________

D. (2 pts). From the UV data alone, which of the following functional groups are ruled out? Cross out your
choices. Assume there could be more than one functional group in the molecule.
O
R
R
R
R
O
R
R C N

E. (1 pt) How many non-equivalent carbon atoms are indicated in the 13C NMR spectrum?

_______

continued

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F. 1. (8 pts) Draw the structure for X 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 X (6 pt penalty).

2. (3 pts) (a) Specify which carbon in your structure gives the peak at 175 ppm in the 13C NMR spectrum.

(b) Specify which carbon in your structure gives the peak at 70 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.

II. (36 pts) Consider the reaction of B in the presence of triethylamine, which leads to A (isomer of B).
(spectral data for A in the Data Tables).

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Hb
Ha
Hc

Et3 N

Hd

[A]

A. (1 pt) In the IR spectrum for B, approx. where would you expect to see the absorption
due to the C=O stretch?
______cm-1
B. (1 pt) In the IR spectrum for B, approx. where would you expect to see the absorption
due to the C=C stretch?
______cm-1
C. (2 pts) What do you predict as max for the UV spectrum of B, considering only * type absorptions?
<200 nm
ca 215 nm
>215 nm
cannot tell ( circle single best answer)
______________________________________________
D. (3 pts) Consider protons Ha and Hb in B.
1. Are they equivalent?
2. What do you predict for their signal(s) in the 1H NMR spectrum [approx. chemical shift and pattern,
including approximate coupling constants]?

_______________________________________________
E. (3 pts) Consider protons Hc and Hd in B.
1. Are they equivalent?
2. What do you predict for their signal(s) in the 1H NMR spectrum [calculated chemical shift and
pattern, including approximate coupling constants]? Show any arithmetic.

F. (2 pts) Consider all of the spectral data and the

mechanism of the reaction to form A, and

continued

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write a [large] structure for A. Draw in
the groups of hydrogens and label groups of
equivalent H as a,b,c, etc.
[if you do not know the structure for A,
you may request it from the proctor for
a cost of 10 pts. Alternatively, you may
answer the following questions in general
terms]
G. (3 pts) Write the steps involved in the formation of A from B in the presence of triethylamine. Be sure to
show the role of the triethylamine.

H. Explain how parts of the 1H NMR spectrum for A are consistent with your structure for A.
1. (2 pts) To which H do you assign the peak at 1.05? Specify the number of Hs giving this peak.
2. (3 pts) To which H do you assign the peak at 1.95? Give number of Hs. Calculate the expected
chemical shift based on your structure and compare with the observed number.

3. (4 pts) To which H do you assign the peaks at 2.20? Give number of Hs.

4. (2 pts) to which H do you assign the pattern at 5.88? Give number of Hs.

I. (2 pts) Explain how the UV data for A is consistent with your structure for A and not with B.

continued

J. (3 pts) Explain how the IR spectrum for A, in the region from 1500-1800 cm-1, is consistent with your
structure. Be as precise as you can in defining the structural type suggested by the IR peak position(s).

____________________________________________________
K. Consider the 13 C NMR spectrum for A.
Re-draw the structure of A here, for reference and
number each carbon.
1. (1 pt) How many non-equivalent carbons are there in A?
5 6 7 8 9 10 11 12
(circle single best answer)
2. (1 pt) To which carbon do you assign the peak at 199?

3. (3 pts) To which carbon do you assign the peak at 160? Explain in terms of the structure how you made
your assignment and take into account the peak at 125 as well.

III. (22 pts)

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A. Consider the actual equilibrium constants for the chair flip of the monosubstituted cyclohexanes, a.
Note that there is not a linear change in Keq with atomic number of halogen atom, and that Cl, Br, and I have similar
effect on Keq.
X

Keq
b

1. (1 pt) Which isomer has the equatorial halogen?

X
F
Cl
Br
I

a ____

Keq
0.53
0.41
0.42
0.42

G (Kcal/mol)
0.25
0.53
0.48
0.47

b______

neither____

2. (2 pts) If X = H, the equilibrium constant Keq would be: zero__ 1.0__ >1.0__ <1.0__
3. (3 pts) Which structure, a or b, is less favorable for X=Cl? Explain carefully the main factor
responsible for the difference.

4. (4 pts) Give your analysis as to why the G for F is less than the G for Cl (expected), but G for Br
and I are about the same as for Cl (not so obvious). Think "outside the box".

B. 1. (4 pts) Use the structure below to draw carefully a diaxial version of 1,3-dichlorocyclohexane. Then
show the ring flip (conformational isomer) structure at the right side of the equilibrium. Considering both
structures, circle neatly any chlorine atoms which are equatorial.

K eq

G = -2.0 Kcal/mol

diaxial
continued

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2. (3 pts) The G for this equlibrium is -2.0 Kcal/mol and Keq is 30. Specify which
is the less stable isomer and explain carefully why it is less stable than the other, in terms of the important types of
repulsive interactions. You may want to re-draw the less stable isomer here.

3. (2 pts) Consider the more stable isomer. Are there any elements of torsional or bond angle strain in
this molecule? Explain.

4. (3 pts) Use the structure below to draw the diaxial version of 1,2-dichlorocyclohexane. Then show the
ring flip (conformational isomer) at the other side of the equilibrium. The G for this process is +0.9 Kcal/mol,
and Keq is ca 0.20. Specify which is the less stable isomer and explain carefully why it is less stable than the other,
comparing repulsive interactions in both isomers.

K eq

diaxial

G = +0.9

Keq = 0.20

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IV. (14 pts) The conformational analysis for cyclohexane derivatives also is useful with related compounds
such as the ketone, cyclohexanone, but with some added features. It gets particularly interesting with several
new dipolar substituents, as in trans-2-chloro-5-methylcyclohexanone with chair conformers a and b.
O

Cl
Keq
O

cyclohexanone

Me
a

in hexane: K eq = 0.3

O
Me

Cl

in methyl alcohol: Keq = 1.4

A. (5 pts) Rationalize why the equilibrium as written is unfavorable in hexane solvent. Analyze
conformers a and b with regard to the usual repulsive interactions as a start, but there is obviously more to it.

B. (3 pts) Rationalize why the reverse is true in methyl alcohol solvent.

C. (6 pts) The infrared spectrum for cyclohexanone shows a strong peak at 1719 cm-1. However, trans-2chloro-5-methylcyclohexanone shows two peaks, at 1745 and 1726 cm-1. Explain carefully the origin of the two
peaks for this compound, including paying attention to the larger change in frequency for one and smaller change
in the other, both toward higher wavenumbers.

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end exam