Proton
NMR
Spectroscopy:
How
to
Identify
Proton
Equivalence




Basic
Vocabulary:


Equivalent
Protons:
protons
that
are
identical
in
every
way.
They
have
the
same
magnetic

environment,
which
gives
them
the
same
spin
flip
energy.

Nonequivalent
Protons:
protons
that
only
have
to
differ
in
a
single
way.
These
protons
do
not

have
the
same
magnetic
environment.





Why
do
we
need
to
identify
proton
equivalence
in
the
first
place?

The
number
of
signals
found
in
the
NMR
spectrum
corresponds
to
the
number
of
nonequivalent

proton
groups
in
the
molecule.
Knowing
how
to
identify
proton
equivalence
will
allow
you
to
identify

nonequivalent
proton
groups
and
identify
the
number
of
signals
that
will
show
up
in
the
NMR
spectrum

for
the
molecule!




 3
NMR
Signals
=
3
different

Inte

 (nonequivalent)
proton
sets


nsity

of


 sign
al


 (Pho
ton


 Qual
ity)






Spin
Flip
Energy
(Photon
Energy)




How
to
determine
Equivalence:


There
are
a
few
different
ways
of
determining
equivalence
that
often
need
to
be
used
together!



1. Identify
a
mirror
plane
in
the
molecule.
If
there
is
symmetry
along
the
mirror
plane
then
the

protons
are
equivalent!










H
 H
 The
green
protons
and
the


 red
protons

are


 




HO C C OH
 symmetrical
along
the


 mirror
plane




 H
 H








2. Identify
an
axis
of
rotation.
If
the
molecule
looks
the
same
upon
rotation,
then
the
protons
are

equivalent!


 Rotate
 Rotate

120
 
 120
 




 







 
 








 


Even
though
the
protons
of
the
methyl

are
rotating
around
the
carbon
(the

yellow,
orange,
and
pink
tabs
help
keep

Molecular
Model
Of: 
 track
of
the
placement!),
the
rotations
do


 not
change
the
molecule
itself.
These


 three
protons
are
equivalent.


In
general,
hydrogens
attached
with



a
single
bond
to
the
same
atom
in
an


 

acyclic
molecule
are
equivalent.


 





3. Lastly,
you
can
identify
what
atoms
the
protons
are
connected
to
and
compare
them.
If
the

atom
that
the
protons

are
directly
connected
are
the
same
move
on
to
identify
the
additional

bonded
to
assure
there
is
no
difference!
If
they
differ
by
even
one
other
atom,
then
they
are

nonequivalent!



Here,
we
already
know
the
hydrogens
of
the
methyl
group
are
equivalent
to
each
other,
and
the

hydrogens
of
the
methylene
group
are
equivalent
to
each
other
because
of
symmetry.
Are
all
the

hydrogens
n
the
molecule
equivalent
to
each
other?





H
 
H

Hydrogens
of
methyl


OH
 Hydrogen
of
the

group
are
directly

alcohol
is
directly

bonded
to
a
carbon.



H
 
H
 bonded
to
oxygen.






Hydrogens
in


 methylene
are
directly

Carbon
is
attached
to


 a
carbon.
 bonded
to
a
carbon.




 

Three
Non‐equivalent

The
carbon
is
attached
to
 groups=
3
signals
on
the

oxygen
and
a
carbon.
 NMR
spectrum



●We
can
immediately
see
that
the
hydrogen
of
the
alcohol
is
non‐equivalent
to
the
rest
because
it
is

directly
attached
to
oxygen
while
the
other
hydrogens
are
attached
to
carbon.



●Since
the
hydrogens
of
the
methyl
and
methylene
group
are
both
attached
to
a
carbon,
we
need
to

look
at
the
atoms
each
carbon
is
bonded
to
in
order
to
correctly
identify
if
they
are
equivalent.
The

carbon
of
the
methyl
group
is
only
attached
to
a
carbon,
but
the
carbon
of
the
methylene
group
is

attached
to
a
carbon
and
oxygen.
Because
they
differ
by
the
addition
of
an
oxygen
atom,
they
are
non‐
equivalent.




Example
Problems:

Determine
the
number
of
signals
that
will
be
found
on
the
NMR
Spectrum
for
each
molecule.




1. 

H
 CH3


F
 CH3


H
 CH3




 

The
protons
of
each
methyl
group
are
equivalent
to
each
other
because
of
the
axis
of
rotation.
The

protons
of
methylene
group
are
equivalent
because
of
their
symmetry.
However,
the
methyl
protons

and
the
methylene
protons
are

non‐equivalent
to
each
other
because
the
atoms
they
are
attached
to

are
not
identical.
The
methyl
protons
are
attached
to
a
carbon,
which
is
attached
to
a
carbon
with
three

additional
carbon
bonds.
The
methylene
protons
are
attached
to
a
carbon
that
is
attached
to
one
other

carbon
and
a
fluorine.


Conclusion:
2
groups
of
non‐equivalent
protons=2
signals
on
the
NMR
Spectrum.




2. 






All
hydrogens
attached
to
a
benzene
ring
are
equivalent.
There
are
three
mirror
planes
in
this

molecule,
and
all
the
hydrogens
are
symmetrical
along
each
one!


**Don’t
let
the
alternating
double
bonds
mess
you
up.
Since
a
benzene
ring
is
in
resonance,
all

the
bonds
have
partial
pi
bond
character,
and
are
therefore
equal!

 Conclusion:
All
hydrogens
are
equivalent=
1
signal
on
the
NMR
Spectrum




3. 


Cl





The
addition
of
the
fluorine
and
chlorine
substituents
to
the
chlorine
rings
destroys
the

symmetry
and
identical
atom
attachment
the
molecule
had
before.


**You
may
be
tempted
to
say
that
the
top
and
bottom
hydrogens
are
symmetrical
and

therefore
equivalent.
However,
if
you
look
at
the
atoms
each
hydrogen
is
bonded
to
it
is

apparent
that
they
are
not
identical.
The
top
hydrogen
is
bonded
to
a
carbon,
which
is
bonded

to
a
carbon
with
a
fluorine
substituent.
The
bottom
hydrogen
is
bonded
to
a
carbon,
which
is

bonded
to
a
carbon
with
a
chlorine
substituent.
The
two
different
halogens
make
the
hydrogens

non‐equivalent.


Conclusion:
4
nonequivalent
hydrogens=4
signals
on
the
NMR
Spectrum





Works
Cited

Image
of
benzene
ring
from:
http://www.daviddarling.info/encyclopedia/B/benzene.html

All
other
information
from
Thinkbook,
pages
133‐139,
and
he
corresponding
lecture.