2014 Fall, Chem 203 Discussion

Nuclear Magnetic Resoance (NMR) Spectrascopy

2.Coupling in
1
H NMR spectra: spin-spin splitting or J coupling
Ya Zhou, 10-13-2014
We have discussed how the chemical shift of an NMR absorption is affected by the magnetic eld B
e

produced by the circulation of neighboring electrons. Now we wish to examine how the magnetic eld
produced by neighboring nuclei B
n
affects the appearance of the
1
H NMR absorption. The effect
occurs through the interaction of nuclear spins with bonding electron spins rather than through space.
Let's rst consider the absorption of a hydrogen nucleus labeled A with only one neighboring
hydrogen nucleus in a vicinal position labeled X. Let's also assume that H
A
and H
X
have signicantly
different chemical shifts.
H
X
will have approximately equal probability of existing in either the low energy alpha state or high
energy beta state. Again because of the small energy difference between the low and high energy
states, the high energy state is easily populated from thermal energy. For those molecules in which
H
X
exists in the low energy state, about half the molecules in the sample, its magnetic eld B
n
will add
to the magnetic eld B
o
-B
e
and for those molecules in which H
X
exists in the higher energy state,
again about half the molecules, its magnetic eld B
n
will subtract from B
o
-B
e
.
1.Chemical shift for
1
H and
13
C (!)
"
#
I. N + 1 Rule.
Ya Zhou, 10-13-2014
J Hz = ppm x MHz (typically 300, 400, or 500 MHz)
The spacing between the lines of a doublet, triplet or quartet is called the coupling constant. It is
given the symbol J and is measured in units of Hertz (cycles per second). The magnitude of the
coupling constant can be calculated by multiplying the separation of the lines in units (ppm) by the
resonance frequency of the spectrometer in megaHertz.
In general, N neighboring protons with the same coupling constant J will split the absorbance
of a proton or set of equivalent protons into N+1 lines. Note that the splitting pattern observed for a
particular proton or set of equivalent protons is not due to anything inherent to that nucleus but due
to the inuence of the neighboring protons. The relative intensity ratios are given by Pascal's
triangle as shown in Figure below.
""
"#
#"
##
"""
""#, "#", #""
"##, #"#,##"
###
###
###
Let's check the cases of of a hydrogen nucleus labeled A with two and three neighboring hydrogen
nucleus in a vicinal position labeled X.
Ya Zhou, 10-13-2014
II. What if neighboring protons with different coupling constant J ?
Jab, Jac are different.
For
a
H:
dd
For
b
H: d
For
a
H: d
c
H
CO
2
H
b
H
a
H
For example, this is an intersting three-membered ring compound produced by pyrethrum owers.
In this molecue, proton
a
H has two neighbours,
b
H and
c
H. The coupling constant J
ab
= 8.0 Hz, and
Jac = 5.5 Hz. The splitting pattern of aH looks like this (right)
a
H
J
ab
= 8.0 Hz
J
ac
= 5.5 Hz
2.0 ppm 2.5 ppm
1
H peak for
a
H ( splitting patern dd)
3. Topicity: Homotopic, Enantiotopic, Diastereotopic.
Practice Question:
(Check the examples from lecture note).
1. Assign the chemical shift to the appropriate proton or group of protons based on their proximity to
an electronegative atome, multiple bond or resonance.
H
3
C
O
CH
3
O
H H
! (ppm)
2.24 (A)
3.61 (B)
A A B
H
3
C
O CH
3
O
H H
H H
! (ppm)
2.18 (D)
2.69 (C)
3.33 (A)
3.63 (B)
D
C
B
A
O H
3
C
O
Si
CH
3
CH
3
CH
3
H H
H H
! (ppm)
0.12 (D)
1.24 (A)
1.89 (C)
4.09 (B)
A
B
C
D
O
H
3
C
CH
3
H
3
C
H
H
H
A
B B
C
C
D
! (ppm)
2.28 (B)
3.71 (A)
6.90 (D)
7.00 (C)
a
H
a
H
a
H
a
H
b
H
b
H
O
0 1 2 3 4
PPM
a
H
b
H
2. Please assign the NMR spectrum peaks of the following molecules, pay attention to the splitting
paterns of each peak.
1
H NMR
1)
Ya Zhou, 10-13-2014
3. Based on the chemical shifts or number of signals, how would you use NMR to distinguish between the
following isomers?
0 100 200
PPM
O
a
b
c
b
a
b
c
13
C NMR
O
O
b
H
Cl
Cl
c
H
a
H
CH
3
a
H
a
H
CH
3
a
H
0 1 2 3 4 5 6 7
PPM
b
H
c
H
a
H
CH
3
O
O Cl
Cl
CH
3
CH
3
0 20 40 60 80 100 120
PPM
a
b
c d
a
b
1
H NMR
13
C NMR
a
b
c
d
2)
Ya Zhou, 10-13-2014
1)
O
CH
3a
CH
3d
O
H
b
H
b
H
c
H
c
O
CH
3a
CH
3d
H
b
H
b
O
H
c
H
c
I
II
Structure I has a C
2
axis of symmetry which causes protons H
a
and H
d
to be in the same
environment, and also H
b
and H
c
. Thus, structrue I would have 2 signals in the NMR spectrum, wihle
structure II gives rise to 4 signals corresponding to each group of H
a,
H
b,
H
c
and H
d
. Protone H
b

in structure II would be shifted farthest downeld due to the next two canbonyl groups.
2) O
H
a
CH
3b
O
CH
3a
H
b
Both I and II have 2 signals in their NMR spectra. Proton H
a
in structure I is an aldehyde proton, so
its signal appears near 10 ppm. On the other hand, the signal for H
b
in structrue II will appear
between 2 -3 ppm. The methyl groups in structure I will be between 1-2 ppm, and the methyl group
in structure II will be between 2-3 ppm.
I
II
3)
O
H
a
H
b
CH
3c
H
d
H
e
H
f
O
H
a
H
b
H
c
CH
3d
H
e
H
f
I
II
There is no symmetry element that causes any of the protons in structure I to be in the same
environment, so 6 signals are observed in the NMR spectrum. Structure II has a C
2
axis symmetry that
makes the H
b
and H
f
protons chemically equivalent, and H
c
and H
e
protons are also equivalent. Thus,
structure II shows 4 signals in the NMR spectrum.
4. Please gure out the highlighted H is homotopic, enantiotopic or diastereotopic.
H H
OH
H
H
3
C H
OH
H
H
3
C
CH
3
Cl
H
H
H
homotopic diastereotopic
enantiotopic
O
Cl
Cl
H H
diastereotopic
CH
3
HO
H
H
H
H
3
C
H H
diastereotopic
Ya Zhou, 10-13-2014
5. Indicate the splitting expected for each hydrogen or group of hydrogens in the following molecules:
O
H
(t)
(tq)
(t)
(tt)
(d)
(t)
1) 2)
N
N
N
N
O
H
3
C
O
CH
3
CH
3
H
(s)
(s)
(s)
(s)
3)
H
3
C
H
H O
O
CH
3
CH
3
CH
3
(d)
(dq)
(d)
(s)
4)
O
CH
3
H
H
H
(dd)
(dd)
(qdd)
(d)
7)
H
H
O
H
H
H
H
H
H
(ddd)
(d)
(d)
(td)
(d)
6. Deduce the structures of the molecules based on their molecular formula, proton NMR spectra,
and any other information given.
O
O H
0 2 4 6 8 10
PPM
1) C
8
H
8
O
2
: not a ester
IHD = 5
Aromatic ring, symmetric, aldehyde, -OCH
3
group
3H
2H
2H
1H
5)
OH O
CH
3
OH O
CH
3
OH O
CH
3
(s)
(d)
(dd)
(dd)
(d)
(s)
(s)
(s)
(s)
(d)
(dd)
(d)
(s)
(d)
(d)
6)
H
H
CH
3
Br
H
3
C Br
H
H
(dt)
(dq)
(d)
(s)
(s)
(d)
(d)
(s)
(d)
Ya Zhou, 10-13-2014
2) C
4
H
6
BrN: contains a nitrile group.( )
IHD = 2
Only one unsaturated triple bond in -CN.
(dd) (dd)
(3-4.5 ppm)
Five possibilities:
(2.5-3 ppm)
H
a
should be more downeld than H
b
, since the bromine group is more electron withdrawing
(or more electronegative) than nitrile group; therefore B is the correct structure.
(dd)
(dd)
(ddq)
(ddq)
C N
CN
CH
3
CN
Br
H
3
C
CN
Br
H
3
C
CN
Br
H
3
C CH
3
CN
Br
Br
Only one methyl group (3 H) in the H-NMR spectrum, therefore A and E are not correct.
A B C D E
CH
3
CN
H
3
C
CN
Br
H
3
C
CN
Br
Br
B C D
(dd) (d)
(d)
The methyl group (3 H) in the H-NMR spectrum is doublet, therefore C is eliminated.
H
3
C
CN
Br
B
(d)
CH
3
CN
Br
D
(d)
B
H
3
C
CN
Br
(d)
H H
H
a
CH
3
NC
Br
D
(d)
H
b
H H
or
0 1 2 3 4
PPM
1H
1H
1H
3H
H
3
C
CN
Br
H
3
C
CN
Br
Ya Zhou, 10-13-2014
N O
O Hb
Hc
Ha
0 1 2 3 4 5 6 7
PPM
7. Assign the chemical shift of the NMR spectrum.
ddt, 1H
dd, 1H
dd, 1H
d, 2H
q, 4H
t, 6H
1.35
3.75
4.50
6.06
5.42
5.28
(ddt)
(dd)
(dd)
a b c
J
ab
> J
ac , because Ha and Hb are trans relationship, while Ha and Hc are cis relationship.
8. How would you use number of signals and signal splitting to distinguish between the following
molecules?
1)
O
Si
H
3
C
O
Si
H
3
C
6 signals 10 signals
(s) (d)
2)
O O
O O
4 signals
3 signals
3)
N
N
4 signals
3 signals
4)
H O
H
O
H O
O
H
H O
O H
3 signals 4 signals
2 signals
H