NMR

1H-NMR
BENZENE RING HYDROGENS
• Ring current causes Ring Current in Benzene
protons attached to
the ring to appear in
the range of 7 to 8
ppm.
Circulating  electrons

• An anisotropy Deshielded
diagram shows the H H
origin of the effect

Bo Secondary magnetic field

generated by circulating 
electrons deshields aromatic
protons
MONOSUBSTITUTED RINGS

ALKYL-SUBSTITUTED
RINGS
SUBSTITUENTS WITH UNSHARED PAI
THE EFFECT OF CARBONYL SUBSTITUEN
 ALKYL-SUBSTITUTED RINGS
In mono-substituted rings with an alkyl substituent
all ring hydrogens come at the same place in the NMR
spectrum.

R
R = alkyl (only)

Apparently the ring current

equalizes the electron density
at all the carbons of the ring
and, therefore, at all of the
hydrogen atoms.
NMR Spectrum of Toluene

5H
CH3
3H
SUBSTITUENTS WITH UNSHARED PAIRS
Electronegative elements with unshared pairs shield
the o- and p- ring positions, separating the hydrogens
into two groups.
.. unshared pair
X
Electron-donating groups
shield the o-, p- positions due to
resonance (see below).

.. ..
X = OH, ..
.. OR, :O R
+
:O R
+
:O R
+
:O R
.. ..
- -
NH2, NR2, : :
..
-O(CO)CH3 ..
..
-
ester
Anisole (400 MHz)

3H
O CH3
Compare:

CH3

The ring protons in

toluene come at
about 7.2 ppm at
the red line.
2H 3H

shielded
THE EFFECT OF CARBONYL SUBSTITUENTS
When a carbonyl group is attached to the ring the
o- and p- protons are deshielded by the anisotropic
field of C=O

R R
O C C O
H H H H

Only the o- protons are in range for this effect.

The same effect is sometimes seen with C=C bonds.

Acetophenone (90 MHz)

CH3 3H
O C
H H
Compare:

CH3

The ring protons in

toluene come at
about 7.2 ppm at
the red line.

2H 3H

deshielded
 para-Disubstitution
1,4-Disubstituted benzene rings will show
a pair of doublets, when the two groups
on the ring are very different

an example:
1-iodo-4-methoxybenzene
 NMR Spectrum of
1-iodo-4-methoxybenzene

3H

I OCH3

CHCl3 impurity
2H 2H
NMR Spectrum of
1-bromo-4-ethoxybenzene

Br OCH2CH3 3H
4H

2H
THE p-DISUBSTITUTED PATTERN CHANGES AS THE
TWO GROUPS BECOME MORE AND MORE SIMILAR
All peaks move closer.
Outer peaks get smaller …………………..… and finally disappear.
Inner peaks get taller…………………………. and finally merge.

X X X

X all H
Y X' equivalent

X=Y X ~ X’ X=X
same groups
NMR Spectrum of
1-amino-4-ethoxybenzene

4H 3H
H2N OCH2CH3

2H
2H
NMR Spectrum of p-Xylene
(1,4-dimethylbenzene)

6H
CH3 CH3

4H
Hydroxyl and Amino Protons
Hydroxyl and amino protons can appear
almost anywhere in the spectrum (H-bonding).

These absorptions are usually broader than

other proton peaks and can often be identified
because of this fact.

Carboxylic acid protons generally appear far

downfield near 11 to 12 ppm.
NMR Spectrum of Ethanol

CH3CH2 OH 3

2 1
SPIN-SPIN DECOUPLING BY EXCHANGE
In alcohols coupling between the O-H hydrogen and
those on adjacent carbon atoms is usually not seen.

This is due to rapid exchange of

C O OH hydrogens between the various

alcohol molecules in the solution.

H H In ultrapure alcohols, however,

coupling will sometimes be seen.

R-O-Ha + R’-O-Hb R-O-Hb + R’-O-Ha

The exchange happens so quickly that the C-H group

sees many different hydrogens on the O-H during the
time the spectrum is being determined (average spin = 0)
 NMR Spectrum of
2-Chloropropanoic Acid

COOH O
1 CH3 CH C OH 3

Cl

1
~12 ppm

offset = 4.00 ppm

UNEQUAL COUPLING
TREE DIAGRAMS

SPLITTING DIAGRAMS
aka “TREE” DIAGRAMS
WHERE DOES THE N+1 RULE WORK ?
The n+1 rule works only for protons in aliphatic chains
and rings, and then under special conditions.

There are two requirements for the n+1 rule to work:

1) All 3J values must be the same all along the chain.
2) There must be free rotation or inversion (rings) to
make all of the hydrogens on a single carbon be
nearly equivalent.
THE TYPICAL SITUATION WHERE THE n+1 RULE APPLIES

Hydrogens can
interchange their
H H H positions by
C C C rotations about
the C-C bonds.
H H H This makes all the
3J = 3J b hydrogens on each
a
of the carbon atoms
All the couplings equivalent.
along the chain
have the same J value.
WHAT HAPPENS WHEN THE J VALUES ARE NOT EQUAL ?

H H H
3J
a = 3J
b C C C
H H H
3J 3J
a b

In this situation each coupling must be considered

independently of the other.

A “splitting tree” is constructed

USE THESE VALUES

H H H
C C C
H H H
7 Hz 3 Hz
CONSTRUCTING A TREE DIAGRAM
SPLITTING FROM
HYDROGENS TO THE LEFT

H H H -CH2-CH2-CH2-
LEVEL ONE
C C C The largest J value
is usually used first.
H H H
Two neighbors gives
a= 7
3J
a triplet.

The next splittings will

Each level of the be added to each leg of
splitting uses the the first splitting.
n+1 rule.
 CONSTRUCTING A TREE DIAGRAM
ADD SPLITTING FROM
HYDROGENS TO THE RIGHT

H H H -CH2-CH2-CH2-

C C C H H H
H H H C C C
3J
a= 7 H H H
3J
b =3
FIRST LEVEL
SECOND LEVEL LEVEL TWO
triplet of triplets
The smaller splitting
is used second.
EACH LEG OF LEVEL ONE IS SPLIT It is also a triplet.
 WHEN BOTH 3J VALUES ARE THE SAME
The n+1 rule is followed …..
LEVEL ONE
Splitting from -CH2-CH2-CH2-
hydrogens on
the left
INTENSITIES
n+1 = (4 + 1) = 5
1:2:1
1:2:1 LEVEL TWO
1:2:1 Splitting from

+ 1:2:1 hydrogens on
the right
1:4:6:4:1

Splittings
overlap ….. because of overlapping legs.
You get the quintet predicted by
the n+1 rule.

WHEN THE n+1 RULE APPLIES WE CAN JUMP TO THE FINAL RESULT - NO TREE NEEDED
 2-PHENYLPROPANAL

A case where there are unequal J values.

 Spectrum of 2-Phenylpropanal
a b d
CH3 CH CHO
J = 7 Hz

c TMS

a
J = 2 Hz
c

b
 7 Hz 2 Hz Rather than the expected
quintet …..
CH3 CH CHO
the methine hydrogen
is split by two different
3J values.

3J
quartet
1 = 7 Hz by -CH3

3J = 2 Hz doublet
2
ANALYSIS by -CHO
OF METHINE
HYDROGEN’S
SPLITTING

quartet of doublets
PURE ETHANOL
ETHANOL 400 MHz

Old sample
Rapid exchange catalyzed
by impurities

hydrogen on OH
is decoupled

HO-CH2-CH3

triplet

broad
quartet singlet
expansion expansion

doublet of triplet
quartets

ETHANOL
Ultrapure sample (new)
Slow or no exchange

400 MHz
triplet
 J=7
J=5 J=7
J=5

triplet quartet of doublets triplet

VINYL ACETATE

ALKENE HYDROGENS
 COUPLING CONSTANTS
PROTONS ON C=C DOUBLE BONDS

3J-cis H H
• = 8-10 Hz

• 3J-trans = 16-18 Hz H

• protons on the same carbon H

2J-geminal = 0-2 Hz
H

For protons on saturated aliphatic chains 3J ~ 8 Hz

NMR Spectrum of Vinyl Acetate

60 MHz
O
CH3 C
O CH CH2
Analysis of Vinyl Acetate
O 3J-trans > 3J-cis > 2J-gem
C H3 C
HC O HB HB HA
C C
HC HA
3J
3J 3J AC
BC BC cis
trans trans
3J 2J 2J
AC AB AB
cis gem gem
2,4-DINITROANISOLE

BENZENE HYDROGENS
 2,4-DINITROANISOLE

400 MHz

9.0 8.0 7.0

2,4-DINITROANISOLE

8.72 ppm 8.43 ppm 7.25 ppm

END