14 - NMR I

spectrum A
3.5
3.0
2.5
2.0
1.5
1.0
spectrum B
3.5
1.30
3.0
1.25
2.5
1.20
1.15
1.10
Chemical Shift (ppm)
2.0
1.5
1.05
1.0
1.00
20.3
5.3
3.2
0.8
-11.8
516.2
503.5
501.1
499.0
496.5
483.9
7.4
511.0
504.2
496.2
489.0
1003.7
996.4
apparent virtual
coupling to A and B
1.0
2.0
1.5
1.0
0.5
A,B
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
7.4
-7.4
1.0
0.9
B A3
1.0
0.1
511.4
504.2
496.2
489.4
453.3
446.4
more lines than

expected
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
A3
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
1D 1H spectrum
6 7
9-12
positive and negative:

H(1) and H(8) COSY
positive: correlation
between H(1) and (2)
irradiated peak
45
negative: exchange
due to OH(7)
1D NOESY spectrum
3.5
3.0
2.5
2.0
1.5
1.0
100.0
0.5
0
-0.5
99.8
0.5
0
-0.5
98.9
0.5
0
-0.5
91.4
0.5
0
-0.5
0.20
0.15
40.2
0.10
0.05
0
-0.05
-0.10
-0.15
-0.20
-0.25 -0.30
9.0
-0.1
0.25
9.7
4.9
31.7
7
0.25
0.20
0.15
0.10
0.05
0
-0.05
-0.10
-0.15
-0.20
-0.25 -0.30
98.0 90.0
5
4
3
137.3
2
143.8
1
13102.7
13092.4
13082.2
160
160
133
132
131
130
129
128
127
158
156
154
155
150
152
145
150
119.0
118.5
118.0
117.5
140
135
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
117.0
125
120
115
80.0
77.5
75.0
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)
Why are there ten signals, not nine?
100 MHz, CDCl3
160
134
133
132
131
130
129
128
127
11899.5
11882.0
11863.7
158
156
154
160
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
140
135
130
126
125
124
123
11258.5
11251.9
11239.4
11232.8
(1)
13102.7
13092.4
13082.2
112.0
111.5
117.0
125
120
10
115
CDCl3
80.0
77.5
75.0
(3)
Why are there ten signals, not nine? The numbering isnt right. Recall the couplings in
fluorobenzene:
N
F
JCF = 245 Hz
JCF = 21
3
JCF = 8
4
JCF = 3
100 MHz, CDCl3
13102.7
13092.4
13082.2
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
coupling:
136
135
134
133
132
131
130
129
128
127
126
125
124
123
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
160
155
150
152
145
150
119.0
118.5
118.0
117.5
140
135
130
11258.5
11251.9
11239.4
11232.8
vicinal coupling
112.0
111.5
117.0
125
120
115
CDCl3
80.0
77.5
75.0
100 MHz, CDCl3
F
3
predicted carbon-13 shifts
137.2
160
149.2
158
156
154
155
150
11899.5
11882.0
11863.7
(4)136 Fluorine
couplings.
135
134
133
132
2 3
160
120.8
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
130
129
128
127
126
Chemical
(ppm)vicinal couplings
3 hasShift
small
3
117.0
149.6
140
135
130
125
124
123
to 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
Shift (ppm)
149.9
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
149.1 Shift (ppm)
149.2
120
115
CDCl3
80.0
77.5
75.0
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
100 MHz, CDCl3
F
1
158
156
154
160
N
1
160
135
155
150
134
133
132
131
130
129
128
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
140
135
130
112.0
111.5
117.0
125
120
115
CDCl3
80.0
77.5
75.0
100 MHz, CDCl3
136
F
1
134
133
132
131
130
129
128
1
9
126
158
156
154
155
150
152
145
150
119.0
118.5
118.0
117.5
140
135
130
125
125
124
123
112.0
111.5
117.0
127
160
135
11899.5
11882.0
11863.7
16017.6
16010.3
16267.9
16260.6
160
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
(7)
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
100 MHz, CDCl3
4
136
F
1
160
134
133
132
131
130
129
128
127
2
N
1
9
158
156
154
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
140
135
130
125
125
124
123
112.0
111.5
117.0
126
11258.5
11251.9
11239.4
11232.8
120
115
CDCl3
80.0
77.5
75.0
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
100 MHz, CDCl3

137.2
9
160
158
136
135
8
3
133
132
131
130
129
128
127
126
125
124
123
156
154
155
134
5 Chemical1Shift (ppm)
F
9
160
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
140
135
130
112.0
111.5
117.0
125
120
115
CDCl3
80.0
77.5
75.0
(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
100 MHz, CDCl3

137.2
1
9
160
2
N
156
154
152
150
134
133
132
131
155
150
145
127
119.0
118.5
118.0
117.5
125.5
140
135
130
125
124
123
112.0
111.5
117.0
125.0
126
124.5
130
129
128
11258.5
11251.9
11239.4
11232.8
135
158
1
9
160
136
126.0
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
124.0
120
123.5
115
123.0
CDCl3
80.0
77.5
75.0
(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
400 MHz, CDCl3
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
1.0
7.5
7.4
2.0
7.3
2.0
7.2
7.1
7.0
6.9
6.8
6.7

14 - NMR I

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14 - NMR I

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spectrum A

more lines than

positive and negative:

Why are there ten signals, not nine?

100 MHz, CDCl3

100 MHz, CDCl3

Chemical Shift (ppm)

100 MHz, CDCl3

predicted carbon-13 shifts

100 MHz, CDCl3

100 MHz, CDCl3

100 MHz, CDCl3

100 MHz, CDCl3

100 MHz, CDCl3

400 MHz, CDCl3

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