Chemistry 303

fall, 1996
SECOND EXAMINATION
7:30 PM, NOVEMBER 5TH, 1996
Duration: 2 hr
Name____________________________________________________________
Lab TA___________________________________________________________
(if you do not know his/her name, give day of lab section)
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:
1___________/35
2___________/14
3___________/27
4___________/07
5___________/07
6.__________/10
Total:

/100

There are 7 pages in this exam; please check now to be sure you have a complete set.
There is also a Data Sheet for Molecule X handed out separately.
Please be aware that a small number of students will be taking the exam at different times up until the afternoon on
Wednesday. It would be well not to discuss the exam until after that time.

PLEDGE:_________________________________________________________________

I. ( 20 pts)
A. (6 pts) Consider the two molecules below. Predict the NMR chemical shift and splitting pattern for
each proton. Show your calculations. (s = singlet, d = doublet, t = triplet, q = quartet)
Cl

Hb

Ha C Cl

Ha C Cl

Cl

Hc
chemical
shift (ppm)
Ha_____
Hb_____
Hc_____

chemical pattern
shift (ppm) (circle)

pattern
(circle)
s,d,t,q,other
s,d,t,q,other
s,d,t,q,other

Ha_____

s,d,t,q,other

Calculations:

B. (3 pts) It should be clear that there is a dependence of the chemical shift position on the number of Cl
substituents. Considering our usual parameters of resonance, inductive, hybridization, and steric effects, what do
you think is the most important parameter in determining the change in chemical shift for these compounds?
Explain.

C. Consider the molecule, cis-1-ethoxypropene, A

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H NMR data: 1.4 ppm, 3H, triplet,

1.9 ppm, 3H, doublet,
3.8 ppm, 2H, quartet,
4.5 ppm, 1H, quintet,
5.9 ppm, 1H, doublet,

J = 7 Hz
J = 7 Hz
J = 7 Hz
J = 7 Hz
J = 7 Hz

H
H

H
C

O
C

13

C NMR data: 9.5, 15.5, 67.0, 101.0, 144.0 ppm

1. (15 pts) Correlate the structure with the 1H NMR data:

a. Show clearly (by labeling as Ha on the structure) the H which show(s) up at
why it (they) appear(s) as a triplet.

1.4, and explain here

b. Show clearly (by labeling as Hb on the structure) the H which show(s) up at 1.9 ppm, and explain
why it (they) appear(s) as a doublet. Use the chemical shift correlation tables to justify your assignment.

c. Show clearly (by labeling as Hc on the structure) the H which show(s) up at

why it (they) appear as a quartet.

3.8 ppm, and explain

d. Show clearly by (labeling as Hd on the structure) the H which show(s) up at

why it (they) appear(s) as a quintet.

4.5 ppm, and explain

e. Show clearly (by labeling as He on the structure) the H which show(s) up at

why it (they) appear(s) as a doublet.

5.9 ppm, and explain

2. (4 pts) Note that a simple alkene, such as cis-2-butene, shows NMR peaks at 1.85 (d, 6H) and 5.4
(q, 2H). Considering our usual parameters of resonance, inductive, hybridization, and steric effects, what do
you think is the most important parameter in determining the difference in chemical shift between the H at
4.5 ppm and the H at 5.9 ppm in molecule A? Explain.

3. (4 pts) Correlate the structure of A with the 13C NMR data: write the chemical shift number next to
the appropriate carbon. It may be helpful to keep in mind your analysis in #2, above. Explain any
ambiguity.

A O

4. (3 pts) How would the 1H NMR spectrum of the trans isomer B

differ from that for the cis isomer, A, above?

B
O
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III. Consider the spectral data for molecule X on the Data Sheet separate from the exam.
A. (5 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)
benzene ring
simple alkenes (consider each case separately)
H

alkynes:

B. (3 pts). From the mass spectral data, what is the molecular weight of the compound?
Give an estimate of the number of carbon atoms.

What common elements are ruled out by the mass spec data alone (cross out your choices): and
explain in one sentence:
H?
N?
O?
F?
Cl?
Br?
I?

C. (3 pts). From the UV data alone, which of the following functional groups are ruled out? Cross out
your choices and explain in a few words.
R

R C N

D. (4 pts) How many non-equivalent carbon atoms are indicated in the C-13 spectrum?
NOTE: one peak falls off to the left of the normal spectral range; it is indicated on the 13C spectrum on a
separate line (above) and the instructions: "offset: 40 ppm". You must add 40 ppm to the peak position of this
peak to get the correct shift.
E. (6 pts) For each set of equivalent protons, give the 1H NMR chemical shift, the relative area, and
describe the splitting pattern including approximate coupling constants. You should estimate the J values as
best you can and indicate whether each is in the range 0-3 Hz, 4-10 Hz, 11-16 Hz, or over 16 Hz.

F. (6 pts) Draw the structure which best fits all the data (review your IR conclusions) and then :
1. Explain in detail how your structure fits the pattern of peaks (splitting pattern) and the coupling
constants.
2. Explain how your structure correlates with the 13C NMR spectral data.
3. Explain how your structure fits the IR spectrum. Mention the two most important correlations.

VI. (10 pts) Consider the isomers, F, G, H. Think about how UV, IR, or NMR could differentiate them.
Respond to the questions below, and give the single most clear-cut feature for each differentiation.
O

F
A.

O
G

Would UV allow you to differentiate F from G?

B. Would UV allow you to differentiate G from H?

C. Would IR allow you to differentiate F from G?

D. Would IR allow you to differentiate G from H?

E. Would 1H NMR allow you to differentiate G from H?

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