Chemistry 303,

fall, 2011

SECOND EXAMINATION
7:30 PM, NOVEMBER 14th, 2011
Duration: 2.0 hr
Name____________________________________________________________
(Print neatly and use your official PU name, the one on your ID.

This is an "open book" examination; you may use anything that is not alive or connected to the Internet.
Note: if you do not know the complete or specific answer, give a partial or general answer-WRITE SOMETHING

If you are using a resonance argument in your answer, draw the relevant resonance structures.

Write only in the space provided for each question.

Score:

p2______/18

p3_______/12

p4_______/14

p5____ _/12

p6_______/12

p7_______/16

p8_______/16
Lab:________/14
Lecture total: _________/100

There are 11 pages in this exam; the last page includes (a) tables of nuclear spin values and for common isotopes, (b) isotope
distributions, and (c) typical coupling constants for 19F, with 13C and 1H.

PLEDGE:_________________________________________________________________

I. (10 pts). Consider the molecule M.

A. (02 pts). What would be the pattern (% height, to 2 significant figures) of peaks in the
molecular ion region of the mass spectrum (M, M+1, M+2, M+3, etc)? You need not
calculate the molecular weight; assume M = 100%. Ignore peaks <1%.

a
S

CH3

B. (02 pts). What would be the approximate position (in cm -1) of the single most diagnostic peak in the IR spectrum?
1650 cm-1

1720 cm-1

What group would give rise to this peak?

C-H

1780 cm-1

1840 cm -1

circle single best answer

CH3-S

circle single best answer

max observed with high

circle single best answer

C=O

C. (02 pts). What do you predict for the UV spectrum (approximately)?

No observable max

max observed with low

D. (02 pts). How many peaks would you expect in the broad band decoupled 13C NMR spectrum? _________
E. (02 pts). What would be the predicted chemical shift in the 1H NMR spectrum for the CH2 group labeled (a) in structure M?
Show your work.

_________________________________________________________________________________________________________
II. (20 pts). Use the spectral techniques (UV, IR, MS, 1H NMR, 13C NMR) to distinguish the pairs of molecules shown.
You may use each technique only once. For each pair, specify one method and clearly describe the single most important difference
that could be used to distinguish the members of each pair. With mass spec, you may not use the high resolution technique to give the
exact molecular formula, and you may not rely on differences in fragmentation pattern. With IR, you may refer only to the region
from 1500-4000 cm-1.

Br

______________________________________________________________________________________________________

O
CF3

CCl3
b

Continued next page--

OMe
OMe
OMe

OMe
b

______________________________________________________________________________________________________
HO

HO

OH

CO2H

O
O
a

______________________________________________________________________________________________________

Ph
Me
a

Me
b

Ph

III. (14 pts). When dissolved in CDCl3, a compound (Y) with the molecular formula C4H8O2 yields the 1H NMR spectrum
below [Hint: CDCl3 can be slightly acidic]. The IR spectrum of Y shows a strong absorption peak at 1720 and a broad peak centered
at 3350 cm-1. Note that the peaks in the 1H NMR spectrum are labeled A,B,C,D.

3H
C
A

1H

D
3H

1H

PPM

A. (06 pts). Draw a structure for this compound,

drawing in all H's. Correlate your structure with the NMR
spectrum shown by labeling each H or group of equivalent
H's with the appropriate letter, A, B, C, D.

B. (02 pts). Explain how your structure is consistent

with the peaks at 1720 and 3350 cm-1 in the IR spectrum.

Y
C. (02 pts). Explain why the proton A shows up with the pattern shown on the spectrum.

D. (04 pts). When Y is stirred in excess D2O, then separated, and the 1H NMR spectrum recorded again in CDCl3, the broad singlet
at 2.80 ppm has disappeared. The rest of the spectrum is the same as before. Explain carefully with pictures why the broad singlet at
2.80 (B) disappears when the molecule is treated with D2O. You need not show a detailed mechanism.

IV. (04 pts). Consider o-hydroxybenzaldehyde (A) and o-methoxybenzaldehyde (B). Note that A shows a C=O stretch at
1670 cm-1 and B has the C=O stretch at 1695 cm -1. Explain why there is the difference in C=O stretching frequency between the two
molecules.
H

O
O

O
O

CH3

V. (04 pts). It often comes up in 1H NMR analysis that you find two peaks of roughly equal intensity near each other in the spectrum.
You are not certain whether these two peaks are singlets arising from two separate and uncoupled protons, or if they are two peaks of
a doublet, arising from two equivalent protons coupled to one other proton. In general, what experiment could you perform to
distinguish clearly between these two possibilities? Explain. The best answer will be an unambiguous and be generally applicable.

VI. (04 pts). Explain why the 1H NMR spectrum of dimethylformamide (M) shows two distinct signals for the methyl groups while
the related structure N shows the two methyl groups as a single peak.
O

H
H

H
N
H3C

Cl
N

CH3

H3C

CH3

VII. (12 pts). The following question engages your knowledge of analyzing resonance structures to explain 1H NMR
chemical shifts. Note the related structures A-D. In each case one of the alkene hydrogens is indicated (HA-HD) along with the 1H
NMR chemical shift for that H, just above it. There is a wide range of chemical shift values.
5.70
HA
Me

Me
A

7.00
HB

Me

4.10
HC
Me

Me

Me

Me

Me

C OMe

A. (04 pts). Using resonance arguments, explain the difference in chemical shift for HA vs H B.

B. (04 pts). Using resonance arguments, explain the difference in chemical shift for H B vs H D.

C. (04 pts). Using resonance arguments, explain the difference in chemical shift for HA vs H C.

6.20
HD
Me

VIII. (16 pts). Summarized below is the 1H NMR spectrum of procaine (P).
(a) 1.06 (t, J = 7 Hz, 3H)
(d) 4.16 (br s, 1H)
(g) 7.84 (d, J = 9 Hz, 1H)

(b) 2.61 (q, J = 7 Hz, 2H)

(e) 4.33 (t, J = 7 Hz, 1H)

(c) 2.82 (t, J = 7 Hz, 1H)

(f ) 6.61 (d, J = 9 Hz, 1H)

A. (3.5 pts). Assign the H in P with the signals listed above. Label each H on the
structure P with the letter (a, b, c) corresponding to the appropriate chemical shift from
the list here. It may be necessary to calculate selected chemical shifts, when possible, to
avoid ambiguous chemical shift assignments. You need not show this work.
B. (3.5 pts). Fill in the third column of this table by indicating which nearby H are
responsible for the coupling patterns. E.g., for the first entry, you will consider the proton
you have assigned as a, and write the letter(s) corresponding to the H(s) it is coupled to.
Label
a
b
c
d
e
f
g

Chemical shift position

1.06
2.61
2.82
4.16
4.33
6.61
7.84

CH2CH3

Which proton(s) coupled to?

H 2C

CH2CH3

CH2
O

O
H

H
H 2N

C. (05 pts). Explain carefully with pictures how you made the chemical shift assignments for the H's on the benzene ring.
[Hint: the chemical shift of benzene in CDCl3 is 7.34 ppm]

D. (04 pts). 1. (02 pts). Procaine is protonated by one equivalent of HCl to give a salt better known
as Novocain, which is used as a local anesthetic in dentistry. What would you predict to be the
structure of Novocain? Explain your choice. Draw using the structure of Procaine on the right.

CH2CH3
N
H 2C
O

CH2
O
H

2. (02 pts). The 1H NMR spectrum of Novocain shows two distinct resonances for the NH protons:
a peak at 4.50 ppm (2H) and peak at 11.2 ppm (1H). Is this spectrum consistent with your
predicted structure? Explain.

CH2CH3

H
H 2N

IX. (16 pts). The following are spectral data for compound Z.
Mass spectrum: m/z = 142 (M+, 100%), 143 (4.7%)
IR: 1792 (s) cm-1 (no other significant peaks in the region 1500-4000 cm-1 other than a set of sp3 C-H stretches)
1

H NMR (CDCl3): 1.40 (t, J = 7.1 Hz, 3H), 4.41 (q, J = 7.1 Hz, 2H)

proton-decoupled 13C NMR (CDCl3): 13.8, 64.6, 115.1 (q, J = 285 Hz), 157.9 (q, J = 42 Hz)
A. (02 pts). What general type of functional group is suggested by the IR spectrum of compound Z?

B. (03 pts). What structural fragment is suggested by the 1 H NMR spectrum of compound Z?

Explain.

C. (06 pts). How many different carbons are contained in compound Z? Please explain the splitting patterns and the
importance of the observed coupling in the proton-decoupled 13C NMR spectrum of compound Z.

D. (05 pts). Propose a structure for compound Z and indicate how the spectral data (mass spectrum, IR, 1H NMR, and 13C
NMR) are compatible with your proposed structure.

X. (14 pts). Lab-Related Question.

A. (06 pts).
1. (04 pts). An orgo lab student reported the melting point range of compound A as 46-51 C and the calibration melting point
range of benzoic acid as 115-119 C. Assuming that the benzoic acid is pure, is the melting point range of compound A reliable, even
with an appropriate correction factor? Why or why not?

2. (02 pts). The observed melting range of compound B is 103-104 C and the observed melting point range for pure benzoic
acid is 123-124 C. What is the corrected melting point range for compound B?

B. (08 pts). Steam distillation of ground cloves affords clove oil, which contains two constituents. The major constituent X,
which is soluble in 5% aqueous NaOH solution, is characterized by the following spectral data:
mass spectrum: m/z = 164 (M, 100%), 165 (11.1%)
IR (liquid film):

3518 (br, s), 3061-2843 (multitude of weak peaks), 1638 (m), 1613 (m), 1607 (m), and 1514 (s) cm-1
[br = broad, m = medium, s = strong]

proton-decoupled 13C NMR (CDCl3): 10 peaks

Choose (circle) the best structure for constituent X from the four possible structures (1-4) shown below. Please give at least one reason
that allowed you to eliminate each of the incorrect structures for X.
O

Reasons:

OH

CH3

CH3

OH
OCH3

CH3

HO

OH

OCH3
1

End exam

10

Table 1. Nuclear spin for common nuclei which are "NMR active".
Nucleus
1
H
2
H
13
C
31
P
19
F
11
B

Spin

Natural abundance
99.98
0.015
1.11
100
100
80

Table 2. Some common isotopes and their abundance

Isotope
1
H
2
H
12
C
13
C
14
N
15
N
16
O
17
O
18
O
32
S
33
S
34
S
35
Cl
37
Cl
79
Br
81
Br
127
I

abundance
99.98
0.015
98.9
1.10
99.6
0.37
99.8
0.038
0.200
95.00
0.76
4.22
75.8
24.23
50.7
49.3
100

Table 3. Some typical coupling constants for 19F and 13C

JC-H 100-130 Hz

H and F on same carbon (geminal)

C

F on carbon adjacent to C and H

JC-F

250-350 Hz

JH-F

80-100 Hz

C
H

JH-F = 15-30 Hz
JC-F = 30-50 Hz

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