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O
CH2 C CH3
RECALL
from last
time
INTEGRATION OF A PEAK
Not only does each different type of hydrogen give a
distinct peak in the NMR spectrum, but we can also tell
the relative numbers of each type of hydrogen by a
process called integration.
Benzyl Acetate
The integral line rises an amount proportional to the number of H in each pea
METHOD 1
integral line
integral
line
55 : 22 : 33
5:2:
simplest ratio
3 the heights
of
58.117 / 11.3
= 5.14
2
21.215 / 11.3
= 1.90
3
33.929 / 11.3
= 3.00
O
CH2 O C CH3
METHOD 2
digital
integration
assume CH3
33.929 / 3 = 11.3
Integrals are
good to about
10% accuracy.
DIAMAGNETIC ANISOTROPY
SHIELDING BY VALENCE ELECTRONS
Diamagnetic Anisotropy
The applied field
induces circulation
of the valence
electrons - this
generates a
magnetic field
that opposes the
applied field.
valence electrons
shield the nucleus
from the full effect
of the applied field
magnetic field
lines
Bo applied
B induced
(opposes Bo)
SPECTRUM
UPFIELD
Highly shielded
protons appear here.
It takes a higher field
to cause resonance.
CHEMICAL SHIFT
CH3
CH3 Si CH3
CH3
Highly shielded
protons appear
way upfield.
TMS
shift in Hz
downfield
Chemists originally
thought no other
compound would
come at a higher
field than TMS.
frequency
h =
2
field
strength
Bo
constants
= ( K) Bo
NMR Field
Strength
1.41 T
2.35 T
7.05 T
H Operating
Frequency
60 Mhz
100 MHz
300 MHz
parts per
million
chemical
=
shift
shift in Hz
= ppm
=
spectrometer frequency in MHz
H Operating
Frequency
60 Mhz
100 MHz
300 MHz
Hz Equivalent
of 1 ppm
n MHz
60 Hz
100 Hz
300 Hz
1
106
= n Hz
ppm
DOWNFIELD
DESHIELDED
UPFIELD
SHIELDED
CHCl3 , H
TMS
12
RCOOH
11
10
RCHO
H
C=C
CH2F
CH2Cl
CH2Br
CH2I
CH2O
CH2NO2
(ppm)
CH2Ar
C-CH-C
CH2NR2
C
CH2S
C-CH2-C
C C-H
C=C-CH2 C-CH3
CH2-CO
R-CH3
R-CH2-R
R3CH
0.7 - 1.3
1.2 - 1.4
1.4 - 1.7
R-C=C-C-H
O
1.6 - 2.6
R-C-C-H
O
2.1 - 2.4
RO-C-C-H
O
2.1 - 2.5
HO-C-C-H
2.1 - 2.5
N C-C-H
2.1 - 3.0
R-C C-C-H
2.1 - 3.0
C-H
R-C C-H
R-N-C-H
2.2 - 2.9
R-S-C-H
2.0 - 3.0
I-C-H
2.0 - 4.0
Br-C-H
2.7 - 4.1
Cl-C-H
3.1 - 4.1
RO-C-H
3.2 - 3.8
HO-C-H
O
3.2 - 3.8
R-C=C-H
4.5 - 6.5
H
6.5 - 8.0
O
R-C-N-H
5.0 - 9.0
O
R-C-H
9.0 - 10.0
O
R-C-O-C-H
3.5 - 4.8
O2N-C-H
4.1 - 4.3
F-C-H
4.2 - 4.8
R-C-O-H
11.0 - 12.0
Ar-N-H
Ar-O-H
DESHIELDING BY
ELECTRONEGATIVE ELEMENTS
Cl
electronegative
element
NMR CHART
deshielded
protons appear
at low field
highly shielded
protons appear
at high field
Electronegativity Dependence
of Chemical Shift
Dependence of the Chemical Shift of CH 3X on the Element X
Compound CH3X
Element X
Electronegativity of X
Chemical shift
most
deshielded
CH3F
CH3OH
CH3Cl
CH3Br
CH3I
CH4
(CH3)4Si
Cl
Br
Si
4.0
3.5
3.1
2.8
2.5
2.1
1.8
4.26
3.40
3.05
2.68
2.16
0.23
TMS
deshielding increases with the
electronegativity of atom X
Substitution Effects on
Chemical Shift
most
deshielded
most
deshielded
-CH2-Br
3.30
-CH2-CH2Br
1.69
The effect
increases with
greater numbers
ppmof electronegative
atoms.
-CH2-CH2CH2Br
1.25
ppm
The effect decreases
with incresing distance.
ANISOTROPIC FIELDS
Bo
Deshielded
generated by circulating
electrons deshields aromatic
protons
fields add
shifted
downfield
C=C
H
Bo
H
H
secondary
magnetic
(anisotropic)
field lines
H
C
C
H
Bo
Shielded
fields subtract
hydrogens
are shielded
secondary
magnetic
(anisotropic)
field
HYDROGEN BONDING
R
O
H
O
R
O R
O
C R
R C
O
H3C O
H
O