INTEGRATION

NMR Spectrum of Phenylacetone

O
CH2 C CH3

RECALL
from last
time

Each different type of proton comes at a different place

You can tell how many different types of hydrogen
there are in the molecule.

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.

Integration = determination of the area

under a peak
The area under a peak is proportional
to the number of hydrogens that
generate the peak.

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

Benzyl Acetate (FT-NMR)

Actually :

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.

Modern instruments report the integral as a number.

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)

fields subtract at nucleus

PROTONS DIFFER IN THEIR SHIELDING

All different types of protons in a molecule
have a different amounts of shielding.
They all respond differently to the applied magnetic
field and appear at different places in the spectrum.

This is why an NMR spectrum contains useful information

(different types of protons appear in predictable places).
DOWNFIELD
Less shielded protons
appear here.

SPECTRUM

UPFIELD
Highly shielded
protons appear here.
It takes a higher field
to cause resonance.

CHEMICAL SHIFT

PEAKS ARE MEASURED RELATIVE TO TMS

Rather than measure the exact resonance position of a

peak, we measure how far downfield it is shifted from TMS
reference compound
tetramethylsilane
TMS

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.

REMEMBER FROM OUR EARLIER DISCUSSION

frequency

h =
2

field
strength

Bo

constants

= ( K) Bo

Stronger magnetic fields (Bo) cause

the instrument to operate at higher
frequencies ( ).

NMR Field
Strength
1.41 T
2.35 T
7.05 T

H Operating
Frequency
60 Mhz
100 MHz
300 MHz

HIGHER FREQUENCIES GIVE LARGER SHIFTS

The shift observed for a given proton

in Hz also depends on the frequency
of the instrument used.
Higher frequencies
= larger shifts in Hz.
TMS
shift in Hz
downfield

THE CHEMICAL SHIFT

The shifts from TMS in Hz are bigger in higher field
instruments (300 MHz, 500 MHz) than they are in the
lower field instruments (100 MHz, 60 MHz).
We can adjust the shift to a field-independent value,
the chemical shift in the following way:

parts per
million

chemical
=
shift

shift in Hz
= ppm
=
spectrometer frequency in MHz

This division gives a number independent

of the instrument used.

A particular proton in a given molecule will always come

at the same chemical shift (constant value).

HERZ EQUIVALENCE OF 1 PPM

What does a ppm represent?
1

H Operating
Frequency
60 Mhz
100 MHz
300 MHz

1 part per million

of n MHz is n Hz

Hz Equivalent
of 1 ppm

n MHz

60 Hz
100 Hz
300 Hz

1
106

= n Hz

ppm

Each ppm unit represents either a 1 ppm change in

Bo (magnetic field strength, Tesla) or a 1 ppm change
in the precessional frequency (MHz).

NMR Correlation Chart

-OH -NH

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

Ranges can be defined for different general types of protons.

This chart is general, the next slide is more definite.

APPROXIMATE CHEMICAL SHIFT RANGES (ppm) FOR SELECTED TYPES OF PROTONS

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

3.0 - 5.0 R-S-H

4.0 - 7.01.0 - 4.0

2.3 - 2.7 R-N-H 0.5 - 4.0

1.7 - 2.7 R-O-H 0.5 - 5.0

YOU DO NOT NEED TO MEMORIZE THE

PREVIOUS CHART
IT IS USUALLY SUFFICIENT TO KNOW WHAT TYPES
OF HYDROGENS COME IN SELECTED AREAS OF
THE NMR CHART
C-H where C
CH on C
is
attached
to
acid
aldehyde benzene alkene
next to aliphatic
C-H
COOH
CHO
CH
=C-H an
pi bonds
electronegaX=C-C-H
tiveX-C-H
atom
12
10
9
7 6
4
3
2
0
MOST SPECTRA CAN BE INTERPRETED WITH
A KNOWLEDGE OF WHAT IS SHOWN HERE

DESHIELDING AND ANISOTROPY

Three major factors account for the resonance
positions (on the ppm scale) of most protons.
1. Deshielding by electronegative elements.
2. Anisotropic fields usually due to pi-bonded
electrons in the molecule.
3. Deshielding due to hydrogen bonding.
We will discuss these factors in the sections that
follow.

DESHIELDING BY
ELECTRONEGATIVE ELEMENTS

DESHIELDING BY AN ELECTRONEGATIVE ELEMENT

Cl

electronegative
element

Chlorine deshields the proton,

that is, it takes valence electron
density away from carbon, which
in turn takes more density from
hydrogen deshielding the proton.

NMR CHART

deshielded
protons appear
at low field

highly shielded
protons appear
at high field

deshielding moves proton

resonance to lower 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

CHCl3 CH2Cl2 CH3Cl

7.27
5.30
3.05

-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

DUE TO THE PRESENCE OF PI BONDS

The presence of a nearby pi bond or pi system

greatly affects the chemical shift.
Benzene rings have the greatest effect.

Ring Current in Benzene

Circulating electrons

Bo

Deshielded

fields add together

Secondary magnetic field

generated by circulating
electrons deshields aromatic
protons

ANISOTROPIC FIELD IN AN ALKENE

protons are
deshielded
Deshielded

fields add

shifted
downfield

C=C
H

Bo

H
H

secondary
magnetic
(anisotropic)
field lines

ANISOTROPIC FIELD FOR AN ALKYNE

H
C
C
H
Bo

Shielded

fields subtract

hydrogens
are shielded

secondary
magnetic
(anisotropic)
field

HYDROGEN BONDING

HYDROGEN BONDING DESHIELDS PROTONS

R
O

H
O
R

O R

The chemical shift depends

on how much hydrogen bonding
is taking place.

Alcohols vary in chemical shift

from 0.5 ppm (free OH) to about
5.0 ppm (lots of H bonding).

Hydrogen bonding lengthens the

O-H bond and reduces the valence
electron density around the proton
- it is deshielded and shifted
downfield in the NMR spectrum.

SOME MORE EXTREME EXAMPLES

O

O
C R

R C
O

Carboxylic acids have strong

hydrogen bonding - they
form dimers.

With carboxylic acids the O-H

absorptions are found between
10 and 12 ppm very far downfield.

H3C O

H
O

In methyl salicylate, which has strong

internal hydrogen bonding, the NMR
absortion for O-H is at about 14 ppm,
way, way downfield.
Notice that a 6-membered ring is formed.