Nuclear Magnetic Resonance Spectroscopy (NMR)
Nuclear Magnetic Resonance Spectroscopy (NMR)
Nuclear Magnetic Resonance Spectroscopy (NMR)
RESONANCE SPECTROSCOPY
(NMR)
Introduction
2
NMR
is the most powerful tool available for organic
structure determination based on their nucleus.
is a physical phenomenon in which nuclei in a
magnetic field absorb and re-emit
electromagnetic radiation.
This ER energy is at a specific resonance frequency
which depends on the strength of the magnetic field and
the magnetic properties of the isotope of the atoms;
in practical applications, the frequency is similar to VHF
and UHF television broadcasts (601000MHz). NMR
allows the observation of specific quantum mechanical
magnetic properties of the atomic nucleus.
=>
Al
27 Si
27
Chapter 13
Nuclear Spin
4
=>
=>
Chapter 13
Chapter 13
Chapter 13
Chapter 13
10
12
E = hv = . Ho / I
v = . Bo / I. h
(2 ,7929) x (5,051 x 10-24) x (14092)
v = --------------------------------------------------
60 MHz
( 6,6256 x 10-27 )x
= 60 x106 Hz =
Magnetic Shielding
13
Shielded Protons
14
=>
15
Protons in a Molecule
(Hydrogen)
Depending on their chemical
environment, protons in a molecule
are shielded by different amounts.
tive,
a
g
e
n
o
r
re elect o the atom
o
m
s
i
Oxygen are attracted t
s
electron
=>
16
17
18
19
Chemical Shift
Chapter 13
20
Chapter 13
21
0 ()
10 ()
- Less shielded
More shielded
Chapter 13
22
Chapter 13
24
Chapter 13
NMR Signals
25
=>
Tetramethylsilane
27
=>
H3C
Si CH3
CH3
Location of Signals
28
More electronegative
atoms deshield more and
give larger shift values.
Effect decreases with
distance.
Additional electronegative
atoms cause increase in
chemical shift due to the
deshielded.
=>
Typical Values
29
Chapter 13
=>
=>
Chapter 13
31
=>
=>
Electronegative
oxygen atom
=>
35
Carboxylic Acid
Proton, 10+
=>
Number of Signals
36
Chapter 13
=>
Intensity of Signals
37
Chapter 13
=>
Chapter 13
=>
Spin-Spin Splitting
39
1,1,2-Tribromoethane
40
Chapter 13
=>
=>
Chapter 13
=>
Chapter 13
The N + 1 Rule
43
=>
Chapter 13
Range of Magnetic
Coupling
44
=>
Chapter 13
46
Splitting for
Isopropyl Groups
=>
Chapter 13
Coupling Constants
47
48
Values for
Coupling Constants
=>
Chapter 13
Complex Splitting
49
a
H
H
C C
Hb
Chapter 13
Splitting Tree
50
a
H
H
C
Hb
Chapter 13
=>
=>
Chapter 13
Stereochemical
Nonequivalence
52
53
Some Nonequivalent
Protons
a
H
H
C C
c
H OHa
dH
Hb
CH3
H
Cl
Hb
aH
Cl
Chapter 13
=>
Hb
Time Dependence
54
Chapter 13
55
Hydroxyl
Proton
Ultrapure samples
of ethanol show
splitting.
Ethanol with a
small amount of
acidic or basic
impurities will not
show splitting.
Chapter 13
=>
N-H Proton
56
=>
Chapter 13
57
Chapter 13
Carbon-13
58
12
=>
Chapter 13
60
Chapter 13
=>
61
Combined 13C
and 1H Spectra
Chapter 13
=>
62
Differences in
13
C Technique
63
Spin-Spin Splitting
Chapter 13
Chapter 13
65
Off-Resonance Decoupling
C nuclei are split only by the protons
attached directly to them.
The N + 1 rule applies: a carbon with N
number of protons gives a signal with
N + 1 peaks.
=>
13
Chapter 13
Interpreting
13
C NMR
66
Two
13
C NMR Spectra
67
=>
Chapter 13
MRI
68
69
End of Chapter 13