Chemistry 303b

fall, 1999

SECOND EXAMINATION
7:30 PM, NOVEMBER 22TH, 1999
Duration: 2.5 hr
Name______________________________KEY______________________________
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:
1___________/16
2___________/18
3___________/27
4___________/18
5___________/21
Total:

/100

There are 10 pages in this exam, followed by three pages of spectra. All 13C NMR spectra are "protondecoupled", as usual. Please check now to be sure you have a complete set.
The last three pages of the exam are Spectra and Spectral data for three molecules, X , Y, and Z. You may detach
these sheets and leave them separate from the exam.
If you are using a resonance argument in your answer, draw the relevant resonance structures.
If you are asked to analyze a structure and you have no idea what it is, do a general analysis of the data for partial
credit.
Please be aware that a small number of students will be taking the exam at different times up until the evening on
Tuesday. It would be well not to discuss the exam until after that time.

PLEDGE:_________________________________________________________________

I. (16 pts) Consider the isomers, F, G, H. Think about how mass spec, UV, IR, or NMR could differen- 2
tiate them. Respond to the questions below, and give the single most clear-cut feature for each differentiation.
OH

OH

A. (2 pts) Would IR allow you to differentiate F from G, assuming you do not have comparison spectra for
each compound?
NO. Without comparison compounds, the fingerprint region is not useful. The functional group
absorption will be the same, or, at best, not different enough to distinguish them. -OH stretch at the same position
for both, about 3300 cm-1

_________________________________________________________________________________________
B. (2 pts) Would IR allow you to differentiate G from H, assuming you do not have comparison spectra for
each compound?
YES.

H will have a C=O stretch/G will no OR

G will have an -OH stretch/H will not

_________________________________________________________________________________________
C. (2 pts)Would Mass Spec allow you to differentiate F from G?
NO, unless you have the actual spectra of one or both compounds for comparison.
Same exact molecular weight.

_________________________________________________________________________________________
D. (3 pts) Would 1H NMR allow you to differentiate F from G?
YES. -CH3 doublet at 0.9 ppm for G is the most distinguishing difference.

3
continued next page

E. (3 pts) Would 1H NMR allow you to differentiate G from H?

YES H has 2 CH3 triplets/G has one -CH3 doublet. must give comparison)
1 pt
2 pts
(other comparisons are possible, but they should be clear-cut)

_________________________________________________________________________________________
F. (2 pts) Would 13C NMR allow you to differentiate F from H.
YES. Presence of downfield (need not specify exact position as long as you make clear it is downfield)
1 pt
2 pts
peak for C=O in H. Not present in F
OR: F shows 4 peaks; H shows 6.

_________________________________________________________________________________________
G. (2 pts) Would 13C NMR allow you to differentiate G from H.
YES. Presence of downfield (need not specify exact position as long as you make clear it is downfield)
1 pt
2pts
peak for C=O in H. Not present in G .

II. (18 pts). Consider the 1H NMR and 13C NMR spectra for dichlorotetrafluoroacetone, Z (p 12). To analyze
the 13C NMR spectrum, it may be useful to look at the structure and generate a possible spectrum and then
look at the actual spectrum to guide a final correlation. Recall the following nuclear spins: 1H, 13C, 19F = 1/2
12C, 16O = 0. [ 35Cl and 37Cl are special but behave as though they have zero spin with regard to coupling.]
A. (2 pts) Is the 1H NMR spectrum consistent with the structure? Explain.
Yes. It is consistent: no peaks and no H in the molecule.
B. (3 pts) Would you predict that the C=O stretching frequency in the IR spectrum of Z to be higher, lower,
or the same frequency as that for acetone? Explain carefully.
X

X
C
Y

O
Y

The stretching frequency of a C=O group is sensitive to the substituents

attached (X,Y). The effects can be analyzed by means of the two
resonance structures shown, with the dipolar form being a minor but
significant contributor. The dipolar structure has a C-O single bond, and
would be expected to have a correspondingly lower stretching frequency.
More contribution from the dipolar form, lower stretching frequence (and
vice versa)

In this case, the highly electron withdrawing groups for X and Y (CF2Cl) will destabilize the dipolar resonance form, making its
contribution less. Therefore the overall structure has more "double bond character", more like the C=O structure, and has a
higher stretching frequence.

C. (1 pt) How many non-equivalent carbons are there in this structure?

(circle single correct answer)

other

4
D. (2 pts) How do you explain the peak at 0 ppm in the 13C NMR spectrum?
It is due to the standard, tetramethylsilane (TMS).
continued next page

E. (2 pts) How do you explain the family of peaks at

78 ppm in the 13C NMR spectrum?

These are the standard peaks for the carbon in the solvent CDCl3, where the D (spin 1) has three spin states
and splits the signal from the C into three peaks of equal height.

F. (4 pts) How do you account for the peaks between 110 and 125 ppm in the 13C NMR spectrum?
Assign to one or more carbons and explain the pattern (relative intensities and peak separations).
These peaks are due to the two equivalent C in the CF2Cl groups. Since F has spin 1/2, the C appears as a triplet,
with the peaks in the ratio (approx) 1:2:1. Big coupling constant, since geminal. [absolute magnitude not an
issue]

G. (4 pts) How do you account for the peaks between 170 and 180 ppm? Assign to one or more carbons
and explain the pattern (relative intensities and peak separations).
The C in the C=O gives this set of peaks, split by 4 equivalent vicinal F. Like H, the F produce a quintet
(n+1) where n=4. Ratio not obvious from the spectrum. The coupling constant is small compared to that in F,
above, because this is a vicinal coupling and the other is geminal.

III. (27 pts) Consider the spectral data for molecule X on p 13.
A. (7 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.): KEY uses bold face for a circle.
carbonyl group (C=O)
_____________________________________________________________________
alcohol (-OH)
____ No peak for -OH stretch in the region 3300 cm-1._______________
amino (-NH 2 )
__No peak for -NH 2 stretch in the region 3300 cm-1
cyano (-CN)
___No peak for the CN triple bond stretch ca 2250 cm-1.______
aldehyde (RCHO)
____No special CH stretch at 2700-2800 cm-1_______
simple alkenes (consider each case separately)
H

H
H

H
R

H
H

R
R

R
H

H
R

R
R

no peak at 1680-1620 cm -1

no peak at 1680-1620 cm -1

should show a weak peak at 1680-1620 cm-1 , but no points were deducted either way (free point)

B. (4 pts). From the mass spectral data, what is the molecular weight of the compound? _116_____
Give an estimate of the number of carbon atoms.
_6 or fewer
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?
Cl and Br are ruled out because each would require a large P+2 peak
I is ruled out because with at. wt 127, it would exceed the MW for the whole cpn.

C. (2 pts). From the UV data alone, which of the following functional groups are ruled out? Cross
out your choices.

R C N

No intense absorption, therefore no conjugated dienes or ketones.

The others cannot be ruled out, but if there is an alkene or alkyne, there must also be something giving rise to
the weak n-pi* absorption.
D. (2 pts) How many non-equivalent carbon atoms are indicated in the C-13 spectrum?

____6___
cont...

E. (5 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
.
0.9
3
triplet
7
_________________________________________________________________________________
1.35
2
sextet
7
_________________________________________________________________________________
1.70
2
quintet
7
_________________________________________________________________________________
2.30
2
triplet
7
_________________________________________________________________________________
3.68
3
singlet
-_________________________________________________________________________________
F. (7 pts) Draw the structure for X which best fits all the data (review your IR conclusions)
1. Explain in detail how your structure fits the pattern of peaks (splitting pattern) 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.
Hb Hb

Ha
Ha
Ha

Ha: unperturbed methyl group 0.9, coupled to 2 adjacent

H (Hb ) with typical 7 Hz coupling. Triplet
Hb: unperturbed CH2 group 1.20, coupled to 5 adjacent
H (Ha, Hc) with typical 7 Hz coupling. Sextet
Hc: CH2 perturbed by -C=O 1.70 calc, coupled to 4
adjacent H (Hb ,Hd ) with typical 7 Hz coupling, quintet
Hd: CH2 perturbed by -C=O 2.30 calc, coupled to 2
adjacent H (Hc) with typical 7 Hz coupling, triplet
He: CH3 perturbed by -OC=O 3.68 calc, coupled to 0
adjacent H, singlet

Hd Hd

Hc H
c

He
He

He

Deduct 1 pt for each wrong assignment,

wrong splitting, wrong explanation
until reach 0 out of 5 total.

2. Explain how your structure correlates with the 13C NMR spectral data. Indicate ambiguous
assignments.
32, fouth
22, second
most upfield
most upfield
C2
C1
13
most upfield

C4
C3

51 furthest downfield sp3 type

O
C5
O

29, third
most upfield

C6
174

No ambiguous assignments

continued next page

3. Explain how your structure fits the IR spectrum, based on the peaks from 4000-1500 cm-1.
C=O stretch at 1740 cm-1 consistent with ester-type carbonyl; no other detectable functionality

IV. (18 pts) Consider the 300 MHz 1H NMR spectrum for molecule Y shown in its entirety on p.11 , and the
list of structures, A-D.
A. (9 pts) Take each structure in turn (except for the correct structure) and point out the most clear-cut
inconsistency between the structure and the spectrum for each of the "wrong" structures. Identify the
correct structure, and proceed to part B, next page. It is in your interest to show your work, such as the
calculation of approx. chemical shifts from the additivity tables, if you use them.
O
Structures:

O
CH2 Cl

H2 C

CH2
HC
Cl

H2 C

CH

CH2
S
B.

CH2

CH2

CH2

CH2

O
CH2

C.

ClH2 CO CH2
H2 C O
O
H2 C O
ClH2 CO CH2 D.

__________________________________________________________________________________________
Structure A:
O

CH2

Cl

CH2
H bC
Cl

CHa

Ha and Hb should be of different chemical shift; also must be far downfield ( 6-8)

__________________________________________________________________________________________
Structure B:
correct

__________________________________________________________________________________________
Structure C:

wrong integration: ratios 2:2:1 instead of the observed 1:1:1

CH2

CH2

CH2

CH2

also: chemical shift for C=CH2 to far down field to match any of the observed.

O
CH2

continued next page

Structure D:
ClCH2O chemical shift is way downfield, compared to any of the observed.

ClH 2CO CH2

H 2C O
O
H 2C O
ClH 2CO CH2

___________________________________________________________________________
B . (9 pts)
1. Redraw the correct structure here.
Label each carbon ( a,b,c...).
O
b
H2C

H2C
c

CH2
d

2 . Correlate the 1H NMR spectrum with the structure.

a. Give the chemical shift and area of each group of equivalent protons. Calculate the
predicted chemical shift for each group by using the Additivity Table for group effects on chemical shifts and
show your work.
b CH 2 - 2H 2.6 calc: 1.2 + 1.10 +
0.30
= 2.6
-C=O
-S
c CH 2 -

2H 3.05 calc: 1.2 +

1.30
-S

0.30
-C=O

= 2.8

d CH 2 -

2H 3.22 calc: 1.2 +

1.30
-S

1.10
-C=O

= 3.6

b. Give the pattern (singlet, doublet, triplet, quartet, quintet, sextet, etc) and approximate
coupling constant for each splitting pattern. Explain the splitting patterns.
b. CH2 triplet due to 2 equiv adjacent H J = 7
c . CH2 triplet due to 2 equiv adjacent H J = 7
d. CH2 singlet due to zero adjacent H

9
3. Correlate the 13C NMR spectrum with the structure as far as you can. Not all peaks can be
assigned unambiguously.
a. C=O at 214 (174 + 40 ppm)
b or c at 26 or 38 ppm (ambiguous)
d. at 39 ppm (most perturbed of the sp3 type C)

V. (21 pts)
A. (3 pts) Draw the most stable and the least stable chair conformers of cis-1,3-dichlorocyclohexane on
the
templates here. Be sure to draw the bonds carefully. Label each chlorine substituent as to whether it is
axial or
equatorial. Indicate which is more stable.
more stable
Cl
Cl
axial

Cl
Cl

equatorial

equatorial

Cl

Cl
axial

B . (3 pts) Describe two different factors which are responsible for the higher energy of the less stable
isomer.
1. there are two additional gauche interactions for the each Cl with the ring CH2
2. There is now a 1,3-diaxial repulsion in the diaxial isomer.

Cl

Cl
1,3-diaxial repulsion

C. (4 pts) In the equilibrium between the chair forms of substituted cyclohexanes, one can calculate the energy
difference, G. For cyclohexanol, the G value is solvent dependent. Explain these data. First discuss the
energy difference in benzene and then compare that with the energy difference in water-MeOH
OH

Keq
OH

G
water-MeOH: 1.25 kcal/mol
benzene: 0.85 kcal/mol

In benzene, the axial OH is less stable due to gauche interactions with ring.
In water-MeOH: H-bonding due to solvent interactions makes the -OH group effectively larger, and inceases the
steric effects, primarily the gauche interaction in axial conformer. That conformer becomes even more destabilized compared to the equatorial conformer.

10

H
O
O

O
H

H
O

continued next page

D. (5 pts) For cis-1,3-dihydroxycyclohexane, the G values for the two chair isomers are shown.
OH
G
water-MeOH: 3.85 kcal/mol
benzene: 0.65 kcal/mol
OH
1. Explain why the value in water-MeOH is larger compared to that for cyclohexanol in waterMeOH. Note that the value is more than twice that for cyclohexanol. Use pictures; draw both chair forms, etc.
As in the dichloro case, the two hydroxy groups have each two gauche interactions (like a single -OH) but in
addition, the 1,3-diaxial repulsion directly between the -OH groups is a special extra destabilization (as with the di
Cl case).

2. Explain why the value in benzene is smaller compared to that for cyclohexanol in water-MeOH.
Use pictures.
In banzene, without special H-bonding to the solvent, the two hydroxy groups can assume internal H-bonding in
the 1,3-diaxial conformation. The gauche interactions are still destabilizing, but the 1,3-interaction now becomes
attractive instead of repulsive.

O
H

The internal H-bonding is in a six membered ring, which is particularly favorable (same for 5-ring, but no others)

E. (5 pts) Analyze the stereochemistry of cis-1-chloro-3-fluorocyclohexane. Draw the most stable chair
form here. Label all stereogenic carbons in your structure as R or S. Draw the mirror image of your
structure.

11
Is the mirror image an: enantiomer,
Cl

diastereomer,

cannot tell
(circle correct ans)
mirror image, non-superimposable
enantiomers

Cl

superimposable

meso

F
S
R

F. (1 pts) What will be the optical rotation for your mirror image structure in part E?
(circle single correct answer)

(+)

(-)

zero

cannot tell