Chemistry 441 Exam 2 key
April 13, 2017
Name______________________
This exam consists of 100 points.
1 12
2 8
3 12
I agree to complete this exam without 4 14
unauthorized assistance from any person, 5 12
materials, or device. 6 34
7 8
____________________________________
Signature and Date
total 100
1. (12 pts) Folate, which is an important cofactor in a number of
enzymatic reactions, has the following structure:
H2N N N H7
R = p-aminobenzoic acid-glutamic acid
N
N R
OH
The 1H signal for the free H7 resonance is at 8.80 ppm. When it binds to
one of its target enzymes, the H7 is now at 9.80 ppm.
a) At 800 MHz (1H frequency), what is the chemical shift difference in Hz
between the free and bound H7 resonance? 800 Hz
b) If the off rate is 220 s-1, how many H7 resonances would be observed if
there was a folate:enzyme ratio of 2:1 (that is, excess free folate)? Note: the
on rate is diffusion controlled (108 s-1M-1) and the off rate dictates the
exchange regime. Coalescence rate = πΔν/√2 or 2.22(Δν). Two resonances
c) At about 100 MHz (1H frequency), what would the H7 resonance look
like (one peak, a coalesced [broad] peak, or two peaks)? One broad peak
220/2.22=99 (about the chemical shift difference
at 100 MHz
1
2. (8 pts) A typical pulse width calibration experiment is shown below.
In this experiment, the spectrum of a strong peak is collected and its
intensity is plotted as function of the pulse width in order to determine
the 90 pulse. The peak nulls around 13 s and again at 25 s. What is
the approximate 90 pulse length? About 6-7 μs
3. (12 pts) Consider the following 13C spin-lattice relaxation time
experiments. Delay time in seconds in plotted along the right hand side
of the spectra.
A. Which carbon has the longest relaxation time (C1, C2, C3, or C4)?
B. Which one has the shortest? C1
C. C1 nulls at 1.2 s. What is its approximate T1 value? =τnull/ln2 or
1.2/0.69 or 1.73 s.
2
4A. (8 pts) Provide an organic structure based on the following 1H and
13C NMR spectra. The 1H splittings: septet, triplet, sextet, doublet,
triplet. Integration: 1:2: 2:6:3.
B. (6 pts) Draw the expected DQF-COSY map for your compound (show
only 3-bond coupling):
3
5. (12 pts) Provide a reasonable organic structure that is consistent with
the following spectra (show all work for full credit).
HO
OH
3 pts for alkyne
3 pts for alcohol(s)
3 pts for methyl(s)
4
6. (34 pts) Provide an organic structure based on the following data sets:
Show all fragments for partial credit (use the COSY, DEPT, and INADEQUATE
to get (DRAW) the pieces)
C10H15BrO
-CH2CH2- 4 pts -CH2CH2CHCHBr 8 pts
C=O 4 pts
Me Me
4 pts -CHBr 4 pts
Me
4 pts
ANSWER:
CH only
Two “up” peaks
CH, CH3 ↑ CH2 ↓
5
Boxes are CH2s
6
Two peaks
Expanded INADEQUATE (from above)
EXAM CONTINUES ONTO THE NEXT PAGE 7
7. (8 pts) Briefly define the following two-dimensional experiments, that
is, indicate the information they provide:
NOESY (1H-1H): Nuclear Overhauser Spectroscopy (2D) through-space
(dipolar) interactions
INADEQUATE: 13C-13C correlation (Incredible Natural Abundance Double
QUAntum Transfer Experiment).
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C shift table:
1
H shift table: