Chemistry 222 Spring 2002

Second Problem Set Due 3/29/02

--ANSWERS
Part A. The proton and carbon NMR spectra shown at the end of the problem set
(marked Part A) came from three compounds (C11H12O2 ) which are all quite similar
isomers of each other.
1) Use the spectral information to propose a structure for the molecules.
E G O G
E G H2C CH2 C CH2
E
H2C CH2 O C CH2 F H2C CH2 F
O CH2 F
H HC H H
A A B
H O
A CH3 H O H O
D B C
H H H3CD
B C H3C D
A1 A2 A3
2) Do a complete data-gathering. You should build a table which has columns for δ,
multiplicity, integral and assignment for each resonance.
A1
Multiplicity Integral (#H's) Assignment Coupled to:
7.7 d 1 A B
7.33 t 1 B A, C
7.0 d 1 C B
3.8 s 3 D [None]
2.9 t 2 E G
2.7 t 2 F G
2.1 quintet 2 G E, F

A2
Multiplicity Integral (#H's) Assignment Coupled to:
8.0 d 1 A B
6.8 d 1 B A
6.7 s 1 C [None]
3.7 s 3 D [None]
2.9 t 2 E G
2.6 t 2 F G
2.1 quintet 2 G E, F
Chemistry 222 Problem Set 2 page 2

A3
Multiplicity Integral (#H's) Assignment Coupled to:
7.1 d 1 A C
6.7 s 1 B [None]
6.65 d 1 C A
3.8 s 3 D [None]
2.9 t 2 E G
2.7 t 2 F G
2.1 quintet 2 G E, F

3) What is the index of hydrogen deficiency for these compounds?

With the formula C11 H12 O2, the IHD is ((2 • 11 + 2) - 12)/2 = 6. This means that there are 6
rings and/or double bonds total. Remember that an aromatic ring is worth 4 (3 for the
double bonds, and 1 for the ring).
4) For assignments, draw a structure of the molecule and use letters to mark the
resonances and the protons from which they came.
See above
5) Explain the coupling patterns seen for each proton.
All of the coupling seen here is normal "simple" multiplets. In each case, the multiplicity
is 1 + the number of neighboring hydrogens listed in the last column of the table.
The most difficult to analyze is the 6.7, 6.65 pair in A3, which was an overlapping singlet
and doublet.
6) Comment on why you made the assignments that you did.
This is a complex problem with a great number of routes to its solution. What follows is a
standard approach, but by no means the only possible way to figure this out.
Let's first look at the common features found in all molecules. This is especially
significant, as the problem states that the molecules are "similar isomers." Starting with
the molecular formula, we see 6 ring/double bond units. The IR shows a carbonyl (strong
peak around 1700 cm-1) and probably an aromatic ring (peaks at 1600, 1500, and around
800 cm-1). These two features account for 5 of the 6 IHD units, meaning that we have to
find only one more ring or double bond. The IR also tells us that there are no OH groups
(alcohol or acid) due to the lack of strong, broad peak around 3300 or so. The proton NMR
confirms an aromatic ring (three protons around 7 ppm) and proves that it is
trisubstituted. There are also some other groupings totalling 9 protons, many of which are
connected to each other (they are multiplets). Looking for common features, there is a 3-
proton singlet at around 3.7 ppm in each spectrum that looks very much like a -O—CH3
group. The remaining hydrogens are in groups of 2 protons each (look at the integrals).
The carbon NMR shows 1 carbonyl peak in each, and it shows 6 aromatic carbons (which
could be alkene carbons also). There are 4 sp3 carbons in each spectrum.
Let's turn the fairly certain structural features into substructures. We know we have a
carbonyl, a tri-substituted aromatic ring, and we strongly suspect a -O—CH3 group.

O H g

C g CH3
g g O
H g
H
Chemistry 222 Problem Set 2 page 3

Note that these add up to C8H6O2, which leaves only C 3H6 from the molecular formula.
Amazingly, C3H6 is the formula for three CH2's.
Note that there is no evidence for a C=C other than the aromatic ring, and we have only
accounted for 5 of the 6 IHD units. That means we need another ring, which is also clear
from the valences of the substructures shown above, along with the 3 CH2's. What do I
mean by this? A divalent substructure like a -CH2- can't end a chain--only continue it. The
OCH3 group can end a chain (for example, one of the free valences on the aromatic ring),
but we have no other, so at least some of the other groups must start at the second free
valence and wrap around to the third.
One of the trickiest decisions is deciding whether or not the OCH3 is by itself somewhere,
or associated with the carbonyl as an ester. The most straightforward argument against
the ester is that it is hard to get the right number of isomers (although A3 is different
enough from A1 and A2 be the one ester]. There is evidence from the carbon-13 NMR
against the ester (carbonyl at about 200 instead of about 165). The evidence from the IR
is weak--it could go either way. The strongest evidence comes from detailed chemical
shift predictions in the proton NMR, which don't work out for the esters, and from
considering the CH 2's, which would be much more similar than they are if they were
attached directly to the ring.
Solving A1
Looking at A1, we have to decide where the groups are. From the coupling analysis, you
can see that the aromatic protons are all together (d, t, d), meaning that all of the
substituents must be together. Also, all of the CH2's are together (the coupling is t,
quintet, t; the center quintet shows that protons G are neighbors to 4 protons, those of E
and F). With the above discussion, it's pretty easy to get close enough for full credit. The
structure marked A1 correct. The structure marked “Not A1” is close, and hard to tell from
the correct one unless you calculate the aromatic shifts from the table I gave you. The
calculated values are shown, establishing that this is the wrong structure (the farthest
downfield peak would be a triplet, rather than one of the doublets as we see for A1). I gave
credit for this incorrect structure. The calculated values for A1 are A: 7.55, B: 7.09, C:
7.05. These are in good qualitative agreement with the spectrum, especially in that the
triplet is in the middle.
E G
H2C CH2 H2C CH2
O CH2 F H2C C O

H O H O
A 6.82
CH3 CH3
H H D H H
B C 7.57 6.75
A1 Not A1

Solving A2
A2 has many similarities to A1. The CH2 region looks virtually identical to A1, so it makes
sense to keep that structural feature intact. The only difference, then, is where the OCH3 is
on the ring. The multiplicity of the aromatic protons give this partly away: with a singlet,
one proton must be isolated, while two are together (both doublets). There are two ways
to do that: the correct way shown below, and the incorrect way shown on the right.
Chemistry 222 Problem Set 2 page 4

E G
H2C CH2 H2C CH2
O C CH2 F O C CH2

H HC H H
A 7.39 7.10

H O O H
B 7.05
H3CD CH3
A2 Not A2
Note that in the compound "Not A2", the singlet is farthest downfield, as opposed to being
farthest upfield in A2. The calculated values for A2 are A: 7.73, B: 6.75, C: 6.76. Again,
this is in decent qualitative agreement with the spectrum.
Solving A3
A3 is a departure from the previous two spectra. Note that the CH2 region has changed;
the unbroken line of CH2's is gone, replaced by a singlet and two triplets. The singlet is
quite a bit downfield (we'll address that later). The aromatic protons are also broken up by
substituents into a group of two neighbors (two doublets) and one isolated H. This last
part is actually quite tricky to see. The clues are that the right-hand "peak" has 2 H's, not
one, and the inner leg is too big to be due to even second-order effects, which affect the
neighboring protons equally. If you look only at the total aromatic proton integral, you
should see that it is 3 H's, the same as the methyl group at 3.7. There clearly are no
triplets in the aromatic region.
The only way to put these together is to have an isolated CH2 somewhere, and a pair of
CH2's somewhere else. But how? Below are three possibilities: A3 and two others.
O O
G H2
C CH2 C CH2 C
E O
H2C CH2 F H2C CH2 C CH2

H H H H H H
A B

H O O H O CH2 H
C
H3C D CH3 H3C

A3 Not A3 Not A3 Too

We can dispose of "Not A3 Too" fairly quickly. The key lies in the chemical shift of the
CH2 bonded both to the aromatic ring and to the O. Since both the O and the aryl ring
would tend to take the resonance downfield, the 2H singlet should be quite a bit downfield
of the 3H singlet, instead of being upfield of it. [Calculated value for that is 4.44 ppm.]
Unfortunately, there is no way that you know of to distinguish between A3 and Not A3.
There are ways, using NMR, but they are beyond the scope of this course.

7) One of the infrared spectra shows a peak at about 1725 cm -1 while the other two
show a peak at 1680 cm-1. What is the molecular origin of that difference?
Chemistry 222 Problem Set 2 page 5

There are two things which affect the frequency of any IR absorbance. One is the weight
of the atoms involved, and the other is the bond strength. Since we are comparing C=O to
C=O, the weights are exactly the same, and can't yield the difference. Bond strength must
be the cause, but why? In this case, two of the ketones are conjugated (A1 and A2) and
one is not (A3). A ketone conjugated to another -system will be weakened by resonance:

O O

To the extent that resonance exists in this system, the C=O is weakened.

Part B. Suppose you were given two unlabeled tubes, each containing OH
one of the two compounds shown to the right. O
1) How would you tell which tube contained which compound by
proton or carbon NMR? Be as explicit as you can. You should
identify and describe at least 3 differences.
A B
I will accept lots of individual variation on this theme. However, the answer has to address
both molecules, and focus on the difference in specific response between them. Here’s a
list of possibilities:
Concept A shows B shows
Proton NMR
=CH2 at ~6 ppm 2 doublets No resonances at 6 ppm
Aromatic H’s 5 of 10 total 4 of 10 total H’s
-CH3 at ~2.5 ppm yes—singlet no singlets in the spectrum
sp 3 H’s only the CH 3 a 1H quintet and a 4H
doublet (or possibly 2 2H
dd’s)
Exchangeable H (OH) 1, which can be washed out No change on treatment
with D2O with D2O
Carbon NMR
# environments 7 6
2
# sp carbon environs at 6 4
~120 ppm
# sp3 environments <100 1 2
ppm
# CH environments (DEPT) 2 4
Chemistry 222 Problem Set 2 page 6

2) How would you tell which tube contained which compound by infrared
spectroscopy? Be as explicit as you can. You should identify and describe at
least 3 differences.
As above.
Concept A shows B shows
OH stretch at 3300 cm-1 yes nothing
C=C stretch at 1600 cm-1 Too hard to tell this from the aromatic resonances that both
compounds have. This wouldn’t work.
C=C bend at ~900 cm-1 Yes No
C-O stretch One, at about 1250 (phenol) Two; one at 1250 and one at
about 1100 cm-1.
“Ring breathing” p-disubstituted: one peak at monosubstituted: two
840-810 peaks at 770-730 and 710-
690

Part C:
1. Predict the number of carbon signals the
compound to the right1 will have in
each chemical shift category (0-50, 50-
100, 100-165, 165-220).
2. Redraw the structure, and identify the O CH3
range into which each carbon should N
fall. H3C CH3
Key: 0-50: 50-100: 100-165:
165+: NA.

1 This is tamoxifen, used to fight breast cancer.

Chemistry 222 Problem Set 2 page 7

Part D: The attached spectrum is for a compound of molecular formula C4 H6 O2 . The

infrared spectrum clearly shows that it contains an ester functional group. Propose a
structure for the compound, and account for the splitting seen in the downfield peaks.

Because of the restricted rotation about the double bond, the coupling relationships
between HA and the other two on the double bond (HB and H C) are not the same. Thus,
rather than making a triplet, the pattern for HA is a doublet of doublets, as shown. Both HB
and HC are also doublet of doublets, but the second coupling (that between HB and H C) is
quite small, and hard to see on this diagram. Usually, gem coupling constants between
vinyl protons are around 3 Hz, as opposed to the 15 or so for trans and the 7-8 for cis
coupling constants.

HB
H3C O C
C C HC
O HA
Chemistry 222 Problem Set 2 page 8

Spectra for Part A.

Compound A1
Chemistry 222 Problem Set 2 page 9

Compound A2:
Chemistry 222 Problem Set 2 page 10

Compound A3: