NMR

(1H-NMR)

SPIN-SPIN SPLITTING
NMR PROBLEMS
 Spin-spin splitting

Often a group of hydrogens will appear as a multiplet

rather than as a single peak.

Multiplets are named as follows:

Singlet Quintet
Doublet Septet
Triplet Octet
Quartet Nonet

This happens because of interaction with neighboring

hydrogens and is called
SPIN-SPIN SPLITTING.
 1,1,2-Trichloroethane
The two kinds of hydrogens do not appear as single peaks,
rather there is a “triplet” and a “doublet”.

integral = 2

Cl H
H C C Cl
integral = 1 Cl H

The subpeaks are due to

triplet doublet spin-spin splitting and are
predicted by the n+1 rule.
 1,1,2-Trichloroethane

integral = 2

Cl H
H C C Cl
integral = 1 Cl H

Where do these multiplets come from ?

….. interaction with neighbors
this hydrogen’s peak these hydrogens are MULTIPLETS
is split by its two neighbors split by their single
neighbor

singlet
doublet
H H H H
triplet
C C C C quartet
H H quintet
sextet
two neighbors
n+1 = 3 one neighbor septet
triplet n+1 = 2
doublet
EXCEPTIONS TO THE N+1 RULE
IMPORTANT !

1) Protons that are equivalent by symmetry

usually do not split one another

X CH CH Y X CH2 CH2 Y

no splitting if x=y no splitting if x=y

2) Protons in the same group

usually do not split one another
H H
more
C H or C detail
H H later
 EXCEPTIONS TO THE N+1 RULE
3) The n+1 rule applies principally to protons in
aliphatic (saturated) chains or on saturated rings.

CH3
CH2CH2CH2CH2CH3 or H

YES YES

but does not apply (in the simple way shown here)
to protons on double bonds or on benzene rings.

H CH3 CH3

H H
NO NO
SOME COMMON SPLITTING PATTERNS

X CH CH Y CH3 CH
(x=y)

CH2 CH CH3 CH2

CH3
X CH2 CH2 Y
CH
(x=y) CH3
NMR Spectrum of Bromoethane

Br CH2CH3
NMR Spectrum of 2-Nitropropane

H
CH3 C CH3
N +
O O-

in higher multiplets the outer peaks

1:6:15:20:16:6:1
are often nearly lost in the baseline
 NMR Spectrum of Acetaldehyde

O
CH3 C
H

offset = 2.0 ppm

 PASCAL’S TRIANGLE
Intensities of
multiplet peaks
1 singlet

The interior
entries are 1 1 doublet
the sums of
the two 1 2 1 triplet

1 3 3 1
numbers
immediately
quartet
above.
1 4 6 4 1 quintet

1 5 10 10 5 1 sextet

1 6 15 20 15 6 1 septet

1 7 21 35 35 21 7 1 octet
THE CHEMICAL SHIFT OF PROTON HA IS
AFFECTED BY THE SPIN OF ITS NEIGHBORS
aligned with Bo opposed to Bo
50 % of +1/2 -1/2 50 % of
molecules molecules
H HA H HA
C C C C

Bo
downfield upfield
neighbor aligned neighbor opposed

At any given time about half of the molecules in solution will

have spin +1/2 and the other half will have spin -1/2.
 SPIN ARRANGEMENTS
one neighbor one neighbor
n+1 = 2 n+1 = 2
doublet doublet

H H H H
C C C C

yellow spins
blue spins

The resonance positions (splitting) of a given hydrogen is

affected by the possible spins of its neighbor.
 SPIN ARRANGEMENTS
two neighbors one neighbor
n+1 = 3 n+1 = 2
triplet doublet

H H H H
C C C C
H H

methine spins
methylene spins
 SPIN ARRANGEMENTS
three neighbors two neighbors
n+1 = 4 n+1 = 3
quartet triplet

H H H H
C C H C C H
H H H H

methylene spins
methyl spins
 THE COUPLING CONSTANT
H H
J
C C H

J J H H

J J
J

The coupling constant is the distance J (measured in Hz)

between the peaks in a multiplet.

J is a measure of the amount of interaction between the

two sets of hydrogens creating the multiplet.
 FIELD COMPARISON
100 MHz 200 Hz

100 Hz
Coupling constants are
constant - they do not
7.5 Hz
change at different J = 7.5 Hz
field strengths

6 5 4 3 2 1
200 MHz
400 Hz
Separation
is larger 200 Hz

The shift is 7.5 Hz

J = 7.5 Hz
dependant
on the field

3 2 1 ppm
100 MHz 200 Hz

100 Hz
J=
7.5 Hz
J = 7.5 Hz

6 5 4 3 2 1
200 MHz Separation 400 Hz
Note the compression of is larger
200 Hz
multiplets in the 200 MHz
spectrum when it is
J = 7.5 Hz
plotted on the same scale
as the 100 MHz spectrum
instead of on a chart which
is twice as wide.

6 5 4 3 2 1 ppm
 50 MHz
J = 7.5 Hz
Why buy a higher
field instrument?

3 2 1
Spectra are
simplified! 100 MHz
J = 7.5 Hz

Overlapping
multiplets are
separated. 3 2 1

200 MHz
Second-order J = 7.5 Hz
effects are
minimized.

3 2 1
NOTATION FOR COUPLING CONSTANTS
The most commonly encountered type of coupling is
between hydrogens on adjacent carbon atoms.

H H This is sometimes called vicinal coupling.

3J It is designated 3J since three bonds
C C intervene between the two hydrogens.

Another type of coupling that can also occur in special

cases is
2J or geminal coupling
H
( most often 2J = 0 )
C H
2J
Geminal coupling does not occur when
the two hydrogens are equivalent due to
rotations around the other two bonds.
 LONG RANGE COUPLINGS
Couplings larger than 2J or 3J also exist, but operate
only in special situations.

H C H
C C
4J , for instance, occurs mainly
when the hydrogens are forced
to adopt this “W” conformation
(as in bicyclic compounds).

Couplings larger than 3J (e.g., 4J, 5J, etc) are usually

called “long-range coupling.”
SOME REPRESENTATIVE COUPLING CONSTANTS
H H
vicinal 6 to 8 Hz three bond 3J
C C
H
trans C C 11 to 18 Hz three bond 3J

H
H H
cis C C 6 to 15 Hz three bond 3J

H
geminal C 0 to 5 Hz two bond 2J
H

Hax Hax,Hax = 8 to 14
Heq Hax,Heq = 0 to 7 three bond 3J

Heq Hax Heq,Heq = 0 to 5

 H
cis 6 to 12 Hz
three bond 3J
trans 4 to 8 Hz
H
H
C 4 to 10 Hz three bond 3J
C H
H
C C 0 to 3 Hz four bond 4J

C H

H C C C 0 to 3 Hz four bond 4J

H
Couplings that occur at distances greater than three bonds are
called long-range couplings and they are usually small (<3 Hz)
and frequently nonexistent (0 Hz).
 TYPES OF INFORMATION
FROM THE NMR SPECTRUM
1. Each different type of hydrogen gives a peak
or group of peaks (multiplet).
2. The chemical shift (d, in ppm) gives a clue as
to the type of hydrogen generating the peak
(alkane, alkene, benzene, aldehyde, etc.)
3. The integral gives the relative numbers of each
type of hydrogen.
4. Spin-spin splitting gives the number of hydrogens
on adjacent carbons.

5. The coupling constant J also gives information

about the arrangement of the atoms involved.
SPECTROSCOPY IS A POWERFUL TOOL

Generally, with only three pieces of data

1) empirical formula (or % composition)

2) infrared spectrum

3) NMR spectrum

a chemist can often figure out the complete

structure of an unknown molecule.
EACH TECHNIQUE YIELDS VALUABLE DATA

FORMULA

Gives the relative numbers of C and H

and other atoms

INFRARED SPECTRUM

Reveals the types of bonds that are present.

NMR SPECTRUM

Reveals the enviroment of each hydrogen

and the relative numbers of each type.
EXAMPLE SPECTRA
FOR DISCUSSION
PART ONE
1 Methyl Ethyl Ketone NMR 07

O
CH3 C CH2CH3
 2 Ethyl Acetate NMR 08

Compare the methylene shift to that of Methyl Ethyl Ketone (previous slide).

O
CH3 C O CH2CH3
3 a-Chloropropionic Acid NMR 04

O
CH3 CH C OH
Cl
4 t-Butyl Methyl Ketone NMR 03
(3,3-dimethyl-2-butanone)

O CH3
CH3 C C CH3
CH3
 5 1-Nitropropane NMR 05

+ O
CH3CH2CH2 N
O-
6 1,3-Dichloropropane NMR 17

Cl CH2CH2CH2 Cl
EXAMPLE SPECTRA
FOR DISCUSSION
PART TWO
7 a-Bromobutyric Acid NMR 09

O
CH3CH2 CH C OH
Br
8 Phenylethyl Acetate NMR 14

O
CH2CH2 O C CH3
 9 Ethyl Succinate NMR 18

O O
CH3CH2 O C CH2CH2 C O CH2CH3
10 Diethyl Maleate NMR 19

O O
CH3CH2 O C C C C O CH2CH3
H H
11 Ethanol NMR 11

CH3CH2 OH
12 Benzyl Alcohol NMR 12

CH2 OH
13 n-Propyl Alcohol NMR 13

CH3CH2CH2 OH