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E. Kwan
Key Questions
(1) What are coupling constants?
Coupling Constants
Eugene E. Kwan
energy
energy diagrams
for J coupling
chemical vs.
magnetic
equivalence
the chemical
shift
virtual coupling
spectrum:
J
Scope of Lecture
Hoye's method
A + J/2
B + J/2
problem
solving
Chem 117
the Fermi
contact
model
what are
typical
couplings?
A - J/2
B - J/2
+10 Hz
H
H
Jortho = +7.5 Hz
8.3
Helpful References
1. Nuclear Magnetic Resonance Spectroscopy... Lambert, J.B.;
Mazzola, E.P. Prentice-Hall, 2004. (Chapter 3)
2. The ABCs of FT-NMR Roberts, J.D. University Science
Books, 2000. (Chapter 10)
3. Spectrometric Identification of Organic Compounds (7th ed.)
Silverstein, R.M.; Webster, F.X.; Kiemle, D.J. Wiley, 2005.
(useful charts in the appendices of chapters 2-4)
4. Organic Structural Spectroscopy Lambert, J.B.; Shurvell,
H.F.; Lightner, D.A.; Cooks, R.G. Prentice-Hall, 1998.
5. Organic Structure Analysis Crews, P. Rodriguez, J.; Jaspars,
M. Oxford University Press, 1998.
4 7
12 15
3 6 9 11 14
1 2 5 8 10 13 16
5 Hz
10 Hz
15 Hz
E. Kwan
Chem 117
spectrum A
3.5
3.0
2.5
2.0
1.5
1.0
spectrum B
3.5
3.0
2.5
2.0
1.5
1.0
I have bolded the protons, since those are the nuclei whose
magnetic resonance frequency we are observing. Carbon-12
has no magnetic moment, so there is no coupling to it. Carbon13 has I=1/2, so there is a doublet which is centered at the
frequency of the 1H-12C peak, but is separated by 1JCH.
(Isotopic substitutions usually only have very small effects on
chemical shifts.)
Q: That's all great, but what exactly do coupling constants
actually correspond to in terms of energy levels and spin
states?
A: It's very complicated, and I defer a more rigorous
discussion till later in the course. For now, take note of this
hand-waving treatment of why line intensities obey Pascal's
triangle for I=1/2 nuclei:
Scenario 1: proton A is adjacent (vicinal) to a proton B.
Only consider the spin states of proton B. It's trivial here:
proton B:
There are only two states and only one way to arrange each
one, so proton A looks like a doublet.
1.30
1.25
1.20
1.15
1.10
Chemical Shift (ppm)
1.05
1.00
E. Kwan
The double intensity for the middle line comes from the fact that
there are two permutations. For a quartet:
Chem 117
A
B
B - J/2
B
A
A - J/2
B
A
transition
every level moves up or down
B
A
energy
by J/4 to produce two doublets
E. Kwan
1
2
symmetric
1
2
1
2
+ J/2
- J/2
- J/2
energy
energy
Chem 117
1
2
J/4
3J/4
antisymmetric
E. Kwan
Chem 117
Uh oh: there are some 10 lines visible! Note that this odd
appearance will not be improved by going to a higher magnetic
field strength. Here's why. This is called an AA'XX' system:
Jcis
HA
FX
HA'
FX'
Jtrans
Although symmetry makes the chemical shifts of protons A and
A' the exact same, proton A has different couplings to FX and FX'
than does A'. So A and A' are not the same, and A and A' can
split each other. There are essentially two different protons with
the same chemical shift coupled to two fluorines. Since J is not
less than the chemical shift difference (0), one gets a strange
spectrum. (Later, we'll see where all these extra lines come
from.) This leads to these definitions:
E. Kwan
What about 3-methylcyclopropene?
H
Me
Me
D
Me
Chem 117
H3C
CH3
CH3
O
CH3
A - J/2
CH3
O
Common sense will tell you what happens when you mix and
match these. For example, 1,2-dichlorobenzene is a AA'XX'
system (why is that?).
B - J/2
AB: two protons are not chemically equivalent, but have similar
chemical shifts
AX: two protons have completely different chemical shifts
AA': two protons are chemically equivalent, but magnetically
non-equivalent
This diagram says that the state is more stable than the
state. But what if J < 0? That seems like an odd thing to say if
one interprets J as the spacing between lines, but with the energy
diagram, it can be understood as:
J>0
J<0
energy
A + J/2
B + J/2
energy
A + J/2
B + J/2
A - J/2
B - J/2
A - J/2
B - J/2
A + J/2
B + J/2
E. Kwan
Pauli exclusion
Si
CH3
CH3CH3
125 Hz
H3C Li
98 Hz
CH3Cl
150 Hz
CH2Cl2
177 Hz
118 Hz
Chem 117
125 Hz
CH3OH
142 Hz
O
137, 150 Hz
162 Hz
O
157 Hz
(olefin)
159 Hz
180 Hz
248 Hz
136 Hz
(For my Chem 106 students, why does MeLi have a very small
one bond C-H coupling constant?)
E. Kwan
Chem 117
Olefin couplings are much smaller (it has been argued that there
are two competing mechanisms which cancel each other out):
CH4
-12.4 Hz
-14.1
CH2Cl2
-7.5 Hz
CH3Cl
-10.5 Hz
Li
TMS
H
H
+3.8 Hz
H
H
+7.4 Hz
H
H
+2.3 Hz
H
H
+1.1 Hz
O
angle effect
-4.4 Hz
CH4
-12.4 Hz
O
-11.0 Hz
+5.5 Hz
O
-5.8 Hz
-14.9 Hz
CH3
-16.9 Hz
-1.8 Hz
-3.2 Hz
H
Jax-ax = 8-13 Hz
H
H
Jax-eq = 1-6 Hz
Jeq-eq = 0-5 Hz
Br
N
CH3
-12.6 Hz
Ph
H
Jtrans = 12-24 Hz
Jax-eq = 3-19 Hz
E. Kwan
Chem 117
Long-Range Couplings
Couplings over four or more bonds are usually small and do not
appear in spectra due to the limitations of linewidth. They can
appear when the coupling is transmitted through -systems:
H
H
H
allylic coupling
-3 to +1 Hz
(-1 Hz typical)
homoallylic
0 to +3 Hz
(2 Hz typical)
H
H
H
H
Jortho = +7.5 Hz
Jpara = +0.7 Hz
Jmeta = +1.4 Hz
W coupling
(all bonds anti)
(-1 to 3 Hz)
H
H
H
U coupling
(unusual)
(0-1 Hz)
+1.7 Hz
+7 Hz
-8.0 Hz
+11.5 Hz
H
H
+19.0 Hz
H
H
+5.6 Hz
H
H
+9.0 Hz
+10 Hz
+18 Hz
H
H
+3.3 Hz
H
H
+4.4 Hz
CH3
F <0.5
8.3
20.3
5.3
3.2
0.8
-11.8
When A and B get too close, A and X look like they're coupled,
but aren't actually coupled. This is called virtual coupling:
X B A
C C C
apparent virtual
coupling to A and B
7.4
511.0
504.2
496.2
489.0
1003.7
996.4
Chem 117
516.2
503.5
501.1
499.0
496.5
483.9
E. Kwan
more lines
than expected
X
1.0
A,B
0.9
0.8
0.7
0.6
0.5
0.4
Chemical Shift (ppm)
0.3
0.2
0.1
1.5
1.0
Chemical Shift (ppm)
0.5
B A3
7.4
-7.4
511.4
504.2
496.2
489.4
453.3
446.4
When the lines get closer together, they get a "roofed" look:
A
X
1.0
0.9
0.8
0.7
0.6
0.5
0.4
Chemical Shift (ppm)
0.3
0.2
0.1
1.0
A3
0.9
0.8
0.7
0.6
0.5
0.4
Chemical Shift (ppm)
0.3
0.2
0.1
E. Kwan
Hoye's Method
If you have a multiplet, you must first determine if it is first- or
second order:
first-order multiplet: use Hoye's method
second-order multiplet: use spectral simulation
The behavior of second-order multiplets is complex and can be
analyzed with the WINDNMR program (available free of charge
from Professor Reich: http://www.chem.wisc.edu/areas/reich/plt/
windnmr.htm). One can predict the coupling patterns for a
variety of guesses and then "fit" the observed pattern. This is
time-consuming but works very well. (This is different from
using empirical or quantum mechanical methods to predict NMR
spectra; those just predict the values of shifts and couplings,
rather than the appearance of the spectrum directly.)
Fortunately, most of the molecules we work with are relatively
unsymmetrical. In the high-powered magnetic fields of modern
spectrometers, they generally give first-order multiplets. Here is
how to extract the couplings from a first-order multiplet. This
method was developed by Hoye (Minneosta) and co-workers:
1
4 7
12 15
3 6 9 11 14
1 2 5 8 10 13 16
line of symmetry
Chem 117
1:3:3:1
1:3:3:1
1:3:3:2:3:3:1
E. Kwan
Chem 117
Hoye's Method
Here is the procedure of Hoye and co-workers:
remember to do
all of this in Hz,
not ppm!
12 15
4 7
3 6 9 11 14
1 2 5 8 10 13 16
5 Hz
these are not couplings;
10 Hz
they are merely distances
15 Hz
to orient us
J1 = J2 = J3 = 5 Hz
J4 = 15 Hz
4 7
12 15
3 6 9 11 14
1 2 5 8 10 13 16
1011.1
1009.3
Chem 117
1017.6
E. Kwan
CO2Me
2.04
2.03
2.02
2.01
Chemical Shift (ppm)
1.5
3
1.0
1.635
1.630
H
H
MeO2C
1.640
CO2Me
MeO2C
H
CO2Me
(2) How many distinct signals should the cis isomer have? What
about the trans isomer?
1.610
1.605
1.600
1.595
1.625
1.620
1.615
Chemical Shift (ppm)
605.8
1.645
588.8
2.0
805.8
1.0
814.1
1.1
594.0
2.5
Chemical Shift (ppm)
2.2
1.99
597.3
3.0
611.0
3.5
602.5
5.8
819.1
2.00
800.6
2.05
812.6
807.3
MeO2C
MeO2C
1.225
1.220
1.215
1.210
1.205
1.200
1.195
Chemical Shift (ppm)
1.190
1.185
1.180
1.175
E. Kwan
Chem 117
MeO2C
CO2Me
MeO2C
CO2Me
CO2Me
MeO2C
CO2Me
CO2Me
MeO2C
MeO2C
MeO2C
CO2Me
MeO2C
H
H
MeO2C
CO2Me
H
CO2Me
CO2Me
CO2Me
MeO2C
MeO2C
CO2Me
MeO2C
CO2Me
H
CO2Me
MeO2C
CO2Me
D
MeO2C
CO2Me
(2) How many distinct signals should the cis isomer have? What
about the trans isomer?
Cis Isomer: There are four protons, but one pair is enantiotopic,
so there should be three signals overall in an "AMX2" or "ABX2"
system, depending on the chemical shift.
Trans Isomer: There are two sets of homotopic, but magnetically
non-equivalent protons. This means an AA'XX' or AA'BB'
system--two signals, but there will definitely be some secondorder behavior in the coupling patterns.
(3) Determine the coupling constants in the spectra above.
The spectra are clearly first-order and therefore Hoye's method
is applicable. This also suggests the cis isomer!
MeO2C
CO2Me
E. Kwan
1002.6
1017.6
1011.1
1009.3
Chem 117
J1 = 1-2 = 6.5
J2 = 1-3 = 8.3
(2) However, spectra are rarely completely first-order or noisefree. So it's common to see couplings be "out of alignment"
by a little bit.
(3) Here, we have this spin system with these averaged
couplings:
2
6.5
8.4
2
2.02
2.01
Chemical Shift (ppm)
1.640
1.635
1.630
605.8
800.6
H
4
8
1.605
1.600
1.595
597.3
J2 = 1-3 = 8.5
J3 = 1-4 = 8.5
1.225
1.220
1.215
1.210
56
1.205
1.200
1.195
Chemical Shift (ppm)
7
1.190
8
1.185
1.180
1.175
H
2
MeO2C
CO2Me
4
34
H
3
H
2
J1 = 1-2 = 5.2
594.0
611.0
J3 = 1-4 = 6.5
1.610
4
5.1
8.4
8.4
J2 = 1-3 = 6.5
56 7
1.625
1.620
1.615
Chemical Shift (ppm)
602.5
1.645
2 34
1.99
J1 = 1-2 = 5.0
805.8
814.1
819.1
2.00
588.8
2.03
807.3
2.04
812.6
2.05
3
5.1
6.5
6.5
3
5.1
6.5
6.5
4
5.1
8.4
8.4
E. Kwan
3
5.1
6.5
6.5
4
5.1
8.4
8.4
H
4
H
3
H
2
Chem 117
An Unknown Structure
Here's another practice question which doesn't involve a lot of
measuring, but does involve a lot of thinking! (This and the final
problem can be found on page 128 of Lambert and Mazzola).
An unknown compound has the molecular formula C6H12O6
and has the following 1D proton NMR spectrum in D2O (solvent
and exchangeable protons are not shown, 300 MHz):
trans: 6.5 Hz
H
2
MeO2C
CO2Me
MeO2C
H
3
4.1
2.1
4.0
3.9
3.8
3.7
3.6
Chemical Shift (ppm)
2.0
3.5
1.0
3.4
3.3
3.2
H 2
E. Kwan
An Unknown Structure
Ask any high school student worth his or her salt what molecule
has the formula C6H12O6, and they'll tell you glucose. So let's
start there:
O
HO
OH
HO
OH
OH
Chem 117
"If it's true, they get all excited, and I let them go on for a while.
Then I point out my counterexample.
OK, what else could it be? I know glucose can exist in a bunch
of forms involving aldehyde intermediates:
HO
HO
OH
OH
OH
HO
OH
HO
O
HO
HO
OH
OH
HO
OH
OH
E. Kwan
An Unknown Structure
The open chain that we have to add a degree of unsaturation to
is this:
OH OH
OH
HO
OH OH
OH
OH
HO
*
OH OH
*
OH OH
HO
OH
HO
OH
HO
OH
HO
OH
HO
OH
OH
The latter is bad news, because that would mean only three
kinds of carbons. Here are all the possibilities. Which of these
is viable?
OH
OH
HO
OH
OH
OH
HO
OH
HO
OH
HO
OH
HO
OH
OH
HO
OH
OH OH
HO
OH
OH
Chem 117
OH
HO
HO
OH
*
OH
myo
OH
OH
OH
OH
OH
muco
OH
scyllo
OH
OH
HO
OH
HO
OH
HO
OH
HO
OH
HO
OH
HO
OH
OH
neo
OH
allo
OH
epi
OH
OH
OH
HO
HO
OH
D-chira
OH
HO
OH
HO
OH
HO
OH
HO
OH
L-chira
OH
OH
OH
cis
E. Kwan
An Unknown Structure
We could sort through the stereoisomers on symmetry grounds,
but it's easier to just guess a structure that has a plane of
symmetry that passes through two vertices. I'll need to
consider the couplings, too:
Couplings (Hz): 1 (2.8x2), 2 (9.6x2), 3 (2.8, 9.6), 4 (9.6x2).
As a reminder, 1 and 4 are worth 1H, while 2 and 3 are worth
2H. This means 1 and 4 lie along the symmetry plane:
OH
H
H 1
HO
HO
4 H
HO
OH
H
H
H
OH
HO
HO
HO
H
H
H
H
OH
H
OH
HO
HO
OH
OH
H1
HO
HO
OH
OH
HO
trans couplings
are large: about
10 Hz
Chem 117
HO
OH
OH
4 H
HO
H
3
E. Kwan
Chem 117
predicted carbon-13 shifts
JCF = 245 Hz
JCF = 21
3
JCF = 8
4
JCF = 3
137.2
13102.7
13092.4
13082.2
F
N
F 124.2
120.8
160.0 154.6
111.6
113.7 N
160.0
130.6
F
111.6
149.2
160
160
133
132
131
130
129
128
Chemical Shift (ppm)
127
158
156
154
Chemical Shift (ppm)
155
150
152
145
150
119.0
118.5
118.0
117.5
Chemical Shift (ppm)
140
135
Chemical Shift (ppm)
130
126
125
124
123
11258.5
11251.9
11239.4
11232.8
134
11899.5
11882.0
11863.7
135
16017.6
16010.3
16267.9
16260.6
136
112.0
111.5
Chemical Shift (ppm)
117.0
125
120
115
80.0
77.5
75.0
Chemical Shift (ppm)
E. Kwan
Chem 117
How many distinct carbon signals are there? There are 9, due to the symmetry plane in the
difluoroaryl ring.
(2)
Does the spectrum have 9 signals in it? Clearly, there are more than 9 signals here due to
carbon-fluorine couplings. First, recognize that the peak near 77 ppm is deuterochloroform,
which is showing a 1:1:1 triplet due to coupling to an I=1 nucleus, deuterium. Next, label the
carbons (blue numbers at the bottom).
(3)
160
158
156
154
Chemical Shift (ppm)
160
134
133
132
131
130
129
128
Chemical Shift (ppm)
127
11899.5
11882.0
11863.7
135
16017.6
16010.3
16267.9
16260.6
136
152
3 4
155
150
145
150
119.0
118.5
118.0
117.5
Chemical Shift (ppm)
140
135
Chemical Shift (ppm)
130
126
125
124
123
11258.5
11251.9
11239.4
11232.8
(1)
13102.7
13092.4
13082.2
112.0
111.5
Chemical Shift (ppm)
117.0
125
120
10
115
CDCl3
80.0
77.5
75.0
Chemical Shift (ppm)
E. Kwan
Chem 117
(3)
F
N
Why are there ten signals, not nine? The numbering isnt right. Recall the couplings in
fluorobenzene:
F
JCF = 245 Hz
JCF = 21
3
JCF = 8
4
JCF = 3
13102.7
13092.4
13082.2
11899.5
11882.0
11863.7
16017.6
16010.3
16267.9
16260.6
F
1
N
1
one-bond coupling
160
158
156
154
Chemical Shift (ppm)
160
155
150
152
145
150
119.0
118.5
118.0
117.5
Chemical Shift (ppm)
140
135
Chemical Shift (ppm)
130
11258.5
11251.9
11239.4
11232.8
At 100 MHz, a 245 Hz coupling is 2.45 ppm. There are four or five notches between the peaks,
which is about right (0.5 ppm/notch). More accurately, this is a doublet of doublets with a
coupling of 16267.9-16017.6 = 250.3 Hz. Thus, this is a one-bond
coupling. The smaller coupling is 7.3 Hz, which is a three-bond/vicinal
136
135
134
133
132
131
130
129
128
127
126
125
124
123
coupling:
Chemical Shift (ppm)
vicinal coupling
112.0
111.5
Chemical Shift (ppm)
117.0
125
120
115
CDCl3
80.0
77.5
75.0
Chemical Shift (ppm)
E. Kwan
Chem 117
137.2
160
120.8
149.2
156
154
Chemical Shift (ppm)
160
11899.5
11882.0
11863.7
2 3
158
155
150
(4)136 Fluorine
couplings.
135
134
133
132
16017.6
16010.3
16267.9
16260.6
F 124.2
160.0 154.6
111.6
113.7 N
160.0
130.6
F
111.6
152
150
119.0
150.1
145
3
117.0
149.6
Chemical Shift (ppm)
140
135
Chemical Shift (ppm)
130
130
129
128
127
126
125
Chemical
Shift
(ppm) vicinal couplings to
3 has
small
124
123
two
fluorines, while 2 doesnt, which is
why it looks fatter (look at the peak
height at half maximum).
118.5
118.0
117.5
Chemical
149.9 Shift (ppm)
149.8
149.7
150.0
131
11258.5
11251.9
11239.4
11232.8
Height of Peaks. Recall that quaternary carbons are often shorter than protonated ones (this is
due to differential relaxation and a lack of nOe enhancment; to be discussed in detail later).
According to the ChemDraw predictions, the only carbons which should be really downfield are
the ones next to nitrogen. One of them is quaternary, and one of them is protonated, which
makes sense if this assignment is made:
13102.7
13092.4
13082.2
(4)
149.5
149.4
125
149.3
112.0
111.5
Chemical
Shift (ppm)
149.1
149.2
120
115
CDCl3
80.0
77.5
75.0
Chemical Shift (ppm)
E. Kwan
Chem 117
Other Fluorine-Coupled Peaks. What are the other peaks? Carbon 8 is a true 1:2:1 triplet with
J = 17.5x2 Hz, which can only happen if it has two geminal (two-bond) couplings to two equal
fluorines. Therefore, it must be the ipso carbon on the fluorinated ring. It also has a very small
height, which makes sense for a quaternary carbon.
13102.7
13092.4
13082.2
F
1
158
156
154
Chemical Shift (ppm)
160
N
1
160
135
155
150
134
133
132
131
130
129
128
Chemical Shift (ppm)
127
11899.5
11882.0
11863.7
16017.6
16010.3
16267.9
16260.6
136
126
7
125
124
123
11258.5
11251.9
11239.4
11232.8
(5)
F
152
145
150
119.0
118.5
118.0
117.5
Chemical Shift (ppm)
140
135
Chemical Shift (ppm)
130
112.0
111.5
Chemical Shift (ppm)
117.0
125
120
115
CDCl3
80.0
77.5
75.0
Chemical Shift (ppm)
E. Kwan
Chem 117
5
136
135
134
133
132
131
F
8
16017.6
16010.3
16267.9
16260.6
160
1
9
158
8
156
154
Chemical Shift (ppm)
155
127
2
N
160
130
129
128
Chemical Shift (ppm)
150
152
145
150
119.0
11899.5
11882.0
11863.7
118.5
118.0
117.5
Chemical Shift (ppm)
140
135
Chemical Shift (ppm)
130
125
125
124
123
112.0
111.5
Chemical Shift (ppm)
117.0
126
11258.5
11251.9
11239.4
11232.8
Other Fluorine-Coupled Peaks. Carbon 9 is quite intense, especially for a peak that has a
splitting in it. It must be ortho to the fluorines. This is an AAXX system, where A and A are
these ortho carbons and X and X are the fluorinesthe carbons and fluorines are chemically
equivalent but magnetically inequivalent and therefore this is a second-order multiplet pattern. It
is reminiscent of an AB quartet. The coupling is approximately 6 Hz, but note that the line
spacing and the actual coupling no longer coincide
directly for a second-order
spectrum.
13102.7
13092.4
13082.2
(6)
120
115
CDCl3
80.0
77.5
75.0
Chemical Shift (ppm)
E. Kwan
Chem 117
Other Fluorine-Coupled Peaks. The only other peak with coupling is 5, which must be the
carbon meta to the fluorines. The couplings are 2x10.3 Hz, which are right for an anti vicinal
coupling.
13102.7
13092.4
13082.2
4
136
F
1
160
134
133
132
131
130
129
128
Chemical Shift (ppm)
127
2
N
1
9
158
156
154
Chemical Shift (ppm)
160
135
155
150
152
145
150
119.0
11899.5
11882.0
11863.7
16017.6
16010.3
16267.9
16260.6
118.5
118.0
117.5
Chemical Shift (ppm)
140
135
Chemical Shift (ppm)
130
125
125
124
123
112.0
111.5
Chemical Shift (ppm)
117.0
126
11258.5
11251.9
11239.4
11232.8
(7)
120
115
CDCl3
80.0
77.5
75.0
Chemical Shift (ppm)
E. Kwan
Chem 117
Pyridine Ring. What remains is to assign carbons 4, 6, and 7. Here is where chemical shift
predictions come in handy again: they show that the carbon para to the pyridine nitrogen should
be the most downfield. But how can 6 and 7 be distinguished?
13102.7
13092.4
13082.2
137.2
9
160
158
135
8
3
133
132
131
130
129
128
Chemical Shift (ppm)
127
126
125
124
123
156
154
155
134
5 Chemical1Shift (ppm)
F
9
160
136
149.2
F
8
120.8
4
1
11899.5
11882.0
11863.7
16017.6
16010.3
16267.9
16260.6
F 124.2
160.0 154.6
111.6
113.7 N
160.0
130.6
F
111.6
11258.5
11251.9
11239.4
11232.8
(8)
150
152
145
150
119.0
118.5
118.0
117.5
Chemical Shift (ppm)
140
135
Chemical Shift (ppm)
130
112.0
111.5
Chemical Shift (ppm)
117.0
125
120
115
CDCl3
80.0
77.5
75.0
Chemical Shift (ppm)
E. Kwan
Chem 117
(9)
F
N
Pyridine Ring. Chemical shifts predict that 6 should be on the left and 7 should be on the right.
Examining an expansion reveals that 6 is much wider than 7, consistent with two unresolved,
small four-bond couplings to fluorine, confirming the predictions. This completes the assignment.
13102.7
13092.4
13082.2
137.2
1
9
160
158
156
154
Chemical Shift (ppm)
152
150
1
9
133
132
131
155
150
145
130
129
128
Chemical Shift (ppm)
127
119.0
118.5
118.0
117.5
Chemical Shift (ppm)
125.5
140
135
Chemical Shift (ppm)
130
125
124
123
112.0
111.5
Chemical Shift (ppm)
117.0
125.0
126
124.5
124.0
Chemical Shift (ppm)
160
134
11258.5
11251.9
11239.4
11232.8
135
126.0
136
149.2
4
6
120.8
final answer
11899.5
11882.0
11863.7
16017.6
16010.3
16267.9
16260.6
F 124.2
160.0 154.6
111.6
113.7 N
160.0
130.6
F
111.6
125
120
123.5
115
123.0
CDCl3
80.0
77.5
75.0
Chemical Shift (ppm)
E. Kwan
Chem 117
(10) Proton Spectrum. We wont bother interpreting this, but I just wanted to point out that although
the proton spectrum is very well resolved, it is a very complex series of partially overlapping
second-order multiplets due to the symmetry, and therefore magnetic inequivalence, of the
fluorines. (This compound came from a Pd-catalyzed cross-coupling of the difluorarylboronic acid
and the 2-chloropyridine, so the sample is more or less regioisomerically pure.
But a mixture of isomeric pyridines, for example, might look like total gibberish!)
F
N
F
1.0
8.7
1.0
8.6
8.5
8.4
8.3
8.2
8.1
8.0
7.9
7.8
7.7
7.6
Chemical Shift (ppm)
1.0
7.5
7.4
2.0
7.3
2.0
7.2
7.1
7.0
6.9
6.8
6.7
Chem 117
115.6
118.8 115.6
148.3
F
142.4
O
31.8
68.5
19.0
121
155.0
154.0
153.5
153.0
152.5
118
152.0
117
116
115
Chemical Shift (ppm)
114
113
112
14980.6
14974.0
15228.7
15221.3
15367.0
15361.9
154.5
119
predicted shifts
15607.8
15601.9
14.1
120
151.5
151.0
150.5
Chemical Shift (ppm)
150.0
149.5
149.0
111
110
14499.0
14495.4
14486.6
14483.7
116.5
11088.7
129.5
112.2
146.3 55.8
136.8
NH2
11413.6
11403.4
151.9
12040.8
12024.0
12020.3
12003.5
118.9
11074.8
11060.1
E. Kwan
148.5
148.0
147.5
147.0
145
144
143
Chemical Shift (ppm)
all peaks
right of arrow
are singlets
152
144
136
128
120
112
104
96
88
80
Chemical Shift (ppm)
72
64
56
48
40
32
24
16
E. Kwan
Chem 117
(1)
O
F
55.8
NH2
11074.8
31.8
NH2
12040.8
12024.0
12020.3
12003.5
68.5
19.0
F
O
14.1
predicted shifts
121
120
119
11088.7
11413.6
11403.4
11060.1
118
A
117
116
115
C
Chemical Shift (ppm)
114
113
112
111
110
155.0
154.5
154.0
153.5
153.0
152.5
152.0
151.5
151.0
150.5
Chemical Shift (ppm)
150.0
149.5
149.0
all peaks
right of arrow
are singlets
152
144
136
128
120
112
104
96
88
80
Chemical Shift (ppm)
148.5
72
14499.0
14495.4
14486.6
14483.7
14980.6
14974.0
15228.7
15221.3
15367.0
15361.9
15607.8
15601.9
148.0
147.5
147.0
145
144
143
Chemical Shift (ppm)
64
56
48
40
32
24
16
Chem 117
151.9
118.9
129.5
112.2
118.8 115.6
148.3
F
116.5
142.4
146.3
136.8
NH2
Number of Peaks. There are two aryl rings, so there should be 12 aryl signals.
However, after accounting for the one-bond coupling in the ipso-fluorocarbons,
there only seem to be 11 carbons! (Dont forget to count 5, which is not part of
any expansion.) Can you resolve this inconsistency?
12040.8
12024.0
12020.3
12003.5
11088.7
(2)
11413.6
11403.4
115.6
11074.8
10
11060.1
E. Kwan
11
predicted shifts
1
155.0
154.5
154.0
153.5
153.0
152.5
152.0
118
151.5
151.0
150.5
Chemical Shift (ppm)
150.0
149.5
149.0
144
136
128
120
112
104
96
88
80
Chemical Shift (ppm)
72
114
113
112
3
148.5
152
117
116
115
Chemical Shift (ppm)
111
110
14499.0
14495.4
14486.6
14483.7
119
14980.6
14974.0
120
15228.7
15221.3
15367.0
15361.9
15607.8
15601.9
121
148.0
147.5
147.0
145
144
143
Chemical Shift (ppm)
64
56
48
40
32
24
16
E. Kwan
Chem 117
118.9
129.5
112.2
118.8 115.6
148.3
F
116.5
142.4
146.3
136.8
NH2
(3)
Fluorine-Carbon Couplings. 4 and 8 are easy: 4 (3.7, 12.4 Hz); 8 (16.8, 20.5). 11
seems to have one 11088.7-11084.3 = 4.4 Hz and two 11088.7-11074.8 = 13.9 Hz
couplings. However, you will see this doesnt really fit the multiplet very well (left). A
better fit (for a first-order multiplet) is 4.4, 12.1x2 Hz, but in both cases, there should
be two central peaks, not one, even accounting for line width. Whats wrong?
14499.0
14495.4
14486.6
14483.7
predicted shifts
140
138
136
134
132
Chemical Shift (ppm)
9
119.5
119.0
130
128
126
118.5
118.0
117.5
117.0 116.5
116.0
Chemical Shift (ppm)
10
115.5
115.0
114.5
114.0
113.5 113.0
124
11074.8
142
122
11064.5
11060.1
144
12040.8
12024.0
12020.3
12003.5
146
11088.7
11084.3
11413.6
11403.4
11
110.5
110.0
Chemical Shift (ppm)
109.5
E. Kwan
Chem 117
(5)
Difluoraryl Ring. The full list of couplings is now: 4 (3.7, 12.4 Hz); 8 (16.8, 20.5); 10
(10.2); 11 (4.4, 24.1). 8 clearly has two geminal couplings and has the right
chemical shift to be the carbon between the fluorines. 11 has one geminal coupling,
O
which means it has to be ortho to a fluorine:
F
predicted shifts
14499.0
14495.4
14486.6
14483.7
142
140
138
136
134
132
Chemical Shift (ppm)
130
128
126
119.0
118.5
118.0
117.5
117.0 116.5
116.0
Chemical Shift (ppm)
11088.7
11084.3
11413.6
11403.4
12040.8
12024.0
12020.3
12003.5
9
119.5
OR
12
11?
144
NH2
124
11074.8
4
146
11064.5
11060.1
11?
11
122
11
10
115.5
115.0
114.5
114.0
113.5 113.0
110.5
110.0
Chemical Shift (ppm)
109.5
E. Kwan
Chem 117
129.5
112.2
118.8 115.6
148.3
F
116.5
142.4
136.8
NH2
O
F
1
11
NH2
O
2
OR
14499.0
14495.4
14486.6
14483.7
predicted shifts
146
144
142
140
138
136
134
132
Chemical Shift (ppm)
130
128
126
9
119.5
119.0
118.5
118.0
117.5
117.0 116.5
116.0
Chemical Shift (ppm)
11088.7
11084.3
12040.8
12024.0
12020.3
12003.5
11413.6
11403.4
12
124
11074.8
11064.5
11060.1
11
122
11
10
115.5
115.0
114.5
114.0
113.5 113.0
110.5
110.0
Chemical Shift (ppm)
109.5
E. Kwan
Chem 117
151.9
129.5
112.2
118.8 115.6
148.3
F
116.5
142.4
146.3
136.8
NH2
O
F
1
11
O
4
3
8
NH2
OR
14499.0
14495.4
14486.6
14483.7
predicted shifts
146
144
142
140
138
136
134
132
Chemical Shift (ppm)
130
128
126
9
119.5
119.0
118.5
118.0
117.5
117.0 116.5
116.0
Chemical Shift (ppm)
11088.7
11084.3
12040.8
12024.0
12020.3
12003.5
11413.6
11403.4
12
124
11074.8
11064.5
11060.1
11
122
11
10
115.5
115.0
114.5
114.0
113.5 113.0
110.5
110.0
Chemical Shift (ppm)
109.5
E. Kwan
Chem 117
(8)
6 Hz wide
F
1
11
120.75
120.50
Chemical Shift (ppm)
120.25
10
3
6
NH2
12
final answer
OR
20 Hz wide
7
121.5
121.0
120.5
8
120.0
9
119.5
119.0
118.5
118.0
117.5
117.0
10
116.5 116.0 115.5 115.0
Chemical Shift (ppm)
114.5
114.0
113.5
11
113.0
112.5
112.0
111.5
111.0
110.5
110.0
E. Kwan
Chem 117
(9)
O
F
Proton Spectrum. With the removal of the symmetry in the difluoroaryl group, the magnetic
inequivalence problem disappears. Can you identify all the peaks?
NH2
F
O
4.9
7.5
7.0
2.0 5.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
Chemical Shift (ppm)
2.0
3.0
2.5
2.0
2.0
1.5
3.0
1.0
0.5