Nuclear Magnetic Resonance

Yale Chemistry 800 MHz

Supercooled Magnet

Bo

Atomic nuclei in
The absence of
a magnetic field

Atomic nuclei in the presence

of a magnetic field
spin - with the field
spin - opposed to the field

The Precessing Nucleus

resonance

spin

spin

Ho

resonance
no resonance

Rf

no resonance

The Precessing Nucleus Again

The Continuous Wave Spectrometer

The Fourier Transform Spectrometer

Observable Nuclei
Odd At. Wt.; s = 1/2
1
13
Nuclei
H1
C6
Abundance (%) 99.98 1.1

Odd At. No.; s = 1

Nuclei

H1

14

N7

Unobserved Nuclei
12

C6

16

O8

32

S16

N7 19F9
0.385 100

15

31

P15 .
100

E = h

h = Plancks constant:1.58x10-37kcal-sec

E = h/2(Bo)

Thus:

= Gyromagnetic ratio: sensitivity

of nucleus to the magnetic field.
1
H = 2.67x104 rad sec-1 gauss-1

= /2(Bo)

For a proton,
if Bo = 14,092 gauss (1.41 tesla, 1.41 T),
= 60x106 cycles/sec = 60 MHz
and
EN = Nh= 0.006 cal/mole

Rf Field vs. Magnetic Field for a Proton

E

60 MHz
100 MHz

1.41 T

2.35 T

E = h/2(Bo)

500 MHz

11.74 T

Bo

Rf Field /Magnetic Field for Some Nuclei

Nuclei
1

13

Rf (MHz)

Bo (T)

/2 (MHz/T)

500.00

11.74

42.58

125.74

11.74

10.71

76.78

11.74

6.54

19

470.54

11.74

40.08

31

202.51

11.74

17.25

Fortunately, all protons are not created equal!

at 1.41 T

60 MHz
60,000,000 Hz

60,000,600 Hz
upfield

downfield

240 Hz

deshielded

10

Me4Si

shielded

60 Hz

0 scale (ppm)

}
at 500 MHz
500 Hz

= (obs - TMS)/inst(MHz) = (240.00 - 0)/60 = 4.00

chemical
shift

Where Nuclei Resonate at 11.74T

12 ppm
2
H
RCO2H

12 ppm
1
H (TMS)

~380 ppm
P (H3PO4)

~220 ppm

31

76.78

220 ppm

F (CFCl3)

19

13

PX3

CPH2

500.00
-SO2F

100

125.74

-CF2-CF2470.54

202.51
R2C=O

CH4

RCH3

200

300

400

500 MHz

Chemical Shifts of Protons

The Effect of Electronegativity on Proton Chemical Shifts

TMS

10

10

CHCl3

CH2Cl2

CH3Cl

CH4

=7.26

=5.30

=3.05

=-0.20

CHBr3

CH2Br2

CH3Br

=6.83

=4.95

=2.68

0
TMS

Chemical Shifts and Integrals

2.2
TMS
area = 3

4.0

area = 2

10

homotopic
protons: chemically
and magnetically
equivalent

enantiotopic protons:
chemically and
magnetically equivalent

Spin-Spin Splitting
= 1.2
area = 9

anticipated spectrum

= 6.4
area = 1

10

TMS

= 4.4
area = 1

Spin-Spin Splitting
= 1.2
area = 9

observed spectrum
= 6.4
area = 1

= 4.4
area = 1
H

10

Jcoupling constant = 1.5 Hz

TMS

J is a constant
and independent
of field

Spin-Spin Splitting
= 6.4

= 4.4

J = 1.5 Hz

J = 1.5 Hz
H

H
local

H
local
observed

observed
8

applied

5
applied

This spectrum is not recorded at ~6 MHz!

and J are not to scale.

Multiplicity of Spin-Spin Splitting for s = 1/2

multiplicity (m) = 2s + 1
# equiv.
neighbors

spin (1/2)

multiplicity

pattern
(a + b)n

symbol

singlet (s)

1/2

1:1

doublet (d)

2/2 = 1

1:2:1

triplet (t)

3/2

1:3:3:1

quartet (q)

4/2 = 1

1:4:6:4:1

quintet (qt)

H NMR of Ethyl Bromide (90 MHz)

CH3CH2Br
for H spins

for H spins

= 1.68
area = 3

= 3.43
area = 2
90 Hz/46 pixels
= 3J/12 pixels
: J= 7.83 Hz

H NMR of Isopropanol (90 MHz)

(CH3)2CHOH
1H septuplet; no coupling to OH
6H, d, J = 7.5 Hz

(4.25-3.80)x90/6 = 7.5 Hz
1H, s

4.25

3.80

Proton Exchange of Isopropanol (90 MHz)

(CH3)2CHOH + D2O

(CH3)2CHOD

Diastereotopic Protons: 2-Bromobutane

Br

homotopic sets
of protons

pro-R
H

H
H

H
H

Diastereotopic protons

pro-S

Diastereotopic Protons: 2-Bromobutane at 90MHz

Br
H

H
H

H
H

1.03 (3H, t)
1.70 (3H, d)
1.82 (1H, m)
1.84 (1H, m)
4.09 (1H, m (sextet?))

H NMR of Propionaldehyde: 300 MHz

H

H
O

1.13 (3H, t, J = 7.3 Hz)

H
H
H

9.79 (1H, t, J = 1.4 Hz)

Is this pattern at 2.46

a pentuplet given that
there are two different
values for J?

No!

H NMR of Propionaldehyde: 300 MHz

2.46
H

H
O

7.3 Hz

7.3 Hz

7.3 Hz

1.4 Hz
H
H
H

7.3 Hz

quartet of doublets

7.3 Hz

9.79 (1H, t, J = 1.4 Hz)

1.13 (3H, t, J = 7.3 Hz)

H NMR of Ethyl Vinyl Ether: 300 MHz

H

= 1.9 Hz

= 6.9 Hz

H
H

3H, t, J = 7.0 Hz

= 14.4 Hz

3.96 (1H, dd, J = 6.9, 1.9 Hz)

4.17 (1H, dd, J = 14.4, 1.9 Hz)
6.46 (1H, dd, J = 14.4, 6.9 Hz)

2H, q, J = 7.0 Hz

6.46

ABX Coupling in Ethyl Vinyl Ether

14.4
6.9

4.17

H
H

1.9

14.4

3.96 (1H, dd, J = 6.9, 1.9 Hz)

3.96

4.17 (1H, dd, J = 14.4, 1.9 Hz)

6.46 (1H, dd, J = 14.4, 6.9 Hz)

Another example

1.9

6.9

Dependence of J on the Dihedral Angle

The Karplus Equation

H NMR (400 MHz): cis-4-t-Butylcyclohexanol

triplet of triplets

He
3.0

3.0

2.7

2.7

He H
e4.03,
4.03,J(H
J(H
)=
3.0
3.0
HzHz
a) a=
J(H
J(H
)=
2.7
2.7
HzHz
e) e=

11.4 Hz
400 Hz

H NMR (400 MHz): trans-4-t-Butylcyclohexanol

triplet of triplets

Ha 3.51, J(Ha) = 11.1 Hz

J(He) = 4.3 Hz

Ha
11.1

11.1

4.3

4.3

30.8 Hz

Peak Shape as a Function of vs. J

10

>> J

~= J

10

9
= 0

10

Magnetic Anisotropy

H
H

Downfield shift for aromatic protons ( 6.0-8.5)

Bo

Magnetic Anisotropy
R
C

C
H

Upfield shift for alkyne protons ( 1.7-3.1)

Bo

13

C Nuclear Magnetic Resonance

13

C Chemical Shifts

WheresWaldo?

Onecarbonin3moleculesofsqualeneis13C

What are the odds that two 13C are bonded to one another?

~10,000 to 1

13

C NMR Spectrum of Ethyl Bromide at 62.8 MHz

JCH = 151 Hz
JCH = 126 Hz

C1

JCH = 3 Hz

C2
JCH = 5 Hz

30

20
26.6

18.3

10
ppm ()

TMS
JCH = 118 Hz

13

C NMR Spectrum of Ethyl Bromide at 62.8 MHz

JCH = 151 Hz

Off resonance decoupling

of the 1H region removes
small C-H coupling.

JCH = 126 Hz

Broadband decoupling
removes all C-H coupling.

C1

C2
JCH = 5 Hz

30

20
26.6

18.3

JCH = 3 Hz

10
ppm ()

TMS
JCH = 118 Hz

13

C Spectrum of Methyl Salicylate

(Broadband Decoupled)

13

C Spectrum of Methyl p-Hydroxybenzoate

(Broadband Decoupled)

The 13C Spectrum of Camphor

The End
F. E. Ziegler, 2004