Chapter 13: HNMR and CNMR guide

Here Id like to give my method on solving NMR questions. I find it easier to go

through all NMR questions in a similar approach. You dont have to use this
approach, and you dont have to go in the specific order, and you can even combine
all the steps, but it provides a good flowchart of the things to look for when
you are given an NMR.

Step 1: Calculate the degrees of freedom! The degrees of freedom are

very helpful in trying to piece together the structure of the compound. To
calculate the degrees of freedom, use the following formula:

For example, to find the degrees of freedom for the structure above, [(7 x 2) + 2 +
1 6 1]/2 = 5
Below Ive written a list of the common usages of degrees of freedom
o Double bond: 1
o Triple bond: 2
o Ring structure: 1
o Benzene ring: (1 x 3 double bonds) + 1 for ring = 4
o Carbonyl compounds (C=O): 1
Keep this in mind when you try to figure out the structure of the
compound. Make sure the compound you draw matches the
number of degrees of freedom!
Step 2: Identify the functional groups that are present in the NMR:
Now look at the NMR and look at where the shifts are. Based on the
location of the shifts, identify the functional groups that are present
in the compound. A picture for Dr. Biewers notes regarding the shift
location is shown below. Memorize this! Keep in mind though that the
shifts are not always absolute! Depending on the adjacent functional
groups near the hydrogen of interest, sometimes functional groups can
be a bit downfield or upfield from the ranges given above. For
example, the benzene ring hydrogen peak will be farther downfield if a

carboxylic acid is on the benzene ring due to the dipole moment pulling more
electron density away, making it more deshielded. However, most of the
time, they are pretty close to the approximate ranges, just dont be
surprised if they are somewhat outside the range.

Also be able to recognize from an alkene which hydrogen is

more downfield and which one is more upfield! Remember that
alkenes are unique and can have different hydrogen signals in a NMR
due to adjacent structures. To determine which alkene hydrogen is
more downfield, use resonance structures! An example is shown
below

Notice that the resonance structures of the compound above places

the carbocation on the 3rd carbon. This suggests that the right
alkene carbon is more electron deficit, and therefore the
hydrogen attached is more electron deficit as well, making it
more downfield than the left alkene hydrogen. The NMR is shown

below.

Step 3: Look at the area of each signal (number of hydrogens), and

look for any planes of symmetry. Look at the number of hydrogens that
are causing each signal and take a note of it. To identify a plane of symmetry,
look for the following
o 1) If the number of hydrogens causing a specific signal is greater than
the number of hydrogens that the specific functional group has, then
there usually is a plane of symmetry SOMEWHERE on at least
the functional group, if not the entire compound. Take below for
example. Note the 18 hydrogens causing that alkane signal. Since you
know that an alkane can hold no more than 3 hydrogens, there
HAS to be a plane of symmetry somewhere in the alkane. In this
case, the plane of symmetry is down the middle of the middle carbon

Another example is shown below. Notice for the carboxylic acid, that
there are 2 hydrogens representing the carboxylic acid peak. Since a
carboxylic acid can only be 1 hydrogen, this means that there
has to be a plane of symmetry dividing the two carboxylic
acids that are causing them to be deshielded the same.

For benzene, if the number of benzene hydrogen signals is less

than the number of benzene hydrogens, then there is a plane
of symmetry around the benzene ring. Looking at the NMR above,
there are 3 distinct signals in the aromatic range, and there are 4
hydrogens. There must be a plane of symmetry around the
benzene ring to compensate for this.
Step 4: Look at the splitting of each signal and also look for specific
splitting patterns: Take a note of each signals splitting pattern.
Remember that the number of peaks a signal is split to is 1 more than the
number of adjacent hydrogens (N+1 rule)! Also, look for specific splitting
patterns, such as
o Ethyl: An ethyl group is shown in a NMR as a quartet of 2
hydrogens and a triplet of 3 hydrogens upfield of the quartet.
The quartet signal will be located within the range of the functional
group, and the triplet will be less deshielded than the quartet. For
example, look at the example below. Notice that in the ethyl
attached to the ester, there is a 2 hydrogen quartet at 4.30,
and a 3 hydrogen triplet further upfield around 1.30
o

Isopropyl: An isopropyl group is shown on a NMR as a 1 hydrogen

septet (7 peak), and a 6 hydrogen doublet upfield of the
septet. An example is shown below

Alkenes: The splitting pattern on alkenes is very unique. Remember

that alkene hydrogens can have different signals due to different
adjacent functional groups. There are complex splitting patterns that
can result from this. Whenever you have a hydrogen that is split
by 2 chemically different hydrogens (such as an alkane and
alkene hydrogen), you will see a more complex splitting
pattern. To determine the number of peaks from splitting that
the hydrogen causes, treat each chemically different hydrogen
separately, then multiply the numbers together. For example, in
the NMR below, instead of splitting into 3 peaks, the first hydrogen will
split the signal to a doublet, and then the second hydrogen will further
split the doublet to another doublet. You will see a series of 4
peaks instead of 3, known as a doublet of doublet. This is shown
in the NMR below. In this case, the left carbon alkene hydrogen is split
by each of the chemically different alkene hydrogen, causing the
doublet of doublets. This is kinda hard to see, and you will rarely
encounter this, but still be able to recognize it if needed. If you
have 2 hydrogens that are chemically equivalent to each other, but
another hydrogen that is chemically different, that will cause a splitting
pattern known as a doublet of triplets.

o
Step 5: Piece together all of the information and draw a structure.
Use all of the information you have deduced to form a structure for the
compound. Make sure it fits all of the information you gather: the degrees
of freedom, the deshielding functional group range, the number of
hydrogens per signal, and the splitting pattern, and most
importantly, the molecular formula! If it doesnt fit, just keep trying. Youll
eventually get it!
It may seem slow know, but keep practicing, and youll eventually get better and
faster at it. Its all about practice! Eventually youll find your own way of doing it
that is proficient and accurate!

CNMR tips

 It goes without saying, memorize the CNMR signal ranges for the
functional groups! A good rule of thumb is taking the HNMR signal
range and multiplying that value by 15-20.

CNMR is mainly used to identify the number of different types of

carbons present. If there are less signals than there are carbons,
then there usually is a plane of symmetry!
The size of the signal is related to the number of hydrogens
attached to the carbon signal. The more hydrogens attached, the
greater the size of the signal
There is usually no splitting observed in a CNMR! However, in a proton
coupled CNMR spectrum, you may see a unique splitting pattern, where
the splitting pattern seen is dependent on the number of hydrogens
DIRECTLY attached to the carbon. (Note that this still uses the N+1
rule, so a carbon that has 3 attached hydrogens would show up as a
quartet, 2 hydrogens = triplet, 1 hydrogen = doublet, and no directly
attached hydrogens = singlet.) Remember that this splitting pattern
only shows up for PROTON COUPLED CNMR!
For Benzene rings, be able to recognize different patterns of 2
identical substituents placed on the benzene ring on different
carbons.

For substituents placed 1,2 to each other, you will see 3 different
benzene carbons

For substituents placed 1,3 to each other, you will see 4 different
benzene carbons

For substituents placed 1,4 to each other, you will see 2 different
benzene carbons

CNMRs are much easier to read than HNMR due to no splitting patterns. You
mainly use it to identify the number of chemically different carbons, any
planes of symmetry or patterns on a benzene ring. If you are able to do that,
then you should be fine with CNMRs.

Example problem
Find the structure of the unknown compound. (There is a doublet at 7.99 and a
doublet at 7.93, quartet at 4.30 and a triplet at 1.29

Step 1: Find the degrees of freedom

[(10 x 2) + 2 10]/2 = 6
Step 2: Identify the functional groups that are present in the NMR
Signal at 11.0 Carboxylic acid (Note that the only signal that can be
greater than 11 is a carboxylic acid)
Signal at 7.99 and 7.93 Most likely benzene hydrogen region (notice that the
signal is at the high end of the benzene ring rang, most likely due to electron
withdrawing groups like carboxylic acid pulling electron density away)
Signal at 4.30 Either an ester or an ether (closer to ester than ether, but can be
both)
Signal at 1.29 either an alpha carbonyl hydrogen or alkane hydrogen
Step 3: Look at the area of each signal (number of hydrogens), and look for any
planes of symmetry
Signal at 11.0 1 hydrogen

Signal at 7.99 and 7.93 Each both 2 hydrogen, for a total of 4 hydrogens. Since
there are only 2 signals, there is a plane of symmetry separating the
benzene ring
Signal at 4.30 2 hydrogen
Signal at 1.29 3 hydrogen
Step 4: Look at the splitting of each signal and also look for specific splitting
patterns
Signal at 11.0 1 hydrogen singlet, meaning no adjacent hydrogens or splitting
Signal at 7.99 and 7.93 Each both 2 hydrogen doublet, meaning there is an
adjacent hydrogen for each signal
Signal at 4.30 2 hydrogen quartet (Notice that this signal and the signal at
1.29 are indicative of an ethyl group, with the ethyl group, with the ethyl
either being a ester or ether ethyl.
Signal at 1.29 3 hydrogen triplet (part of the ethyl group)
Step 5: Piece together all of the information and draw a structure
Lets start with the benzene ring. We see 4 benzene ring hydrogens, meaning that
there are 2 substituents attached. We see one carboxylic acid signal and an ethyl
signal. Since the ethyl group has to be at the very end of a compound, this means
that the ethyl and the carboxylic acid are separate substituents attached
to the benzene ring. Since there are two different substituents attached to the
ring, in order to achieve the 2 doublet signal branching pattern, they must be
placed 1,4 to each other, In any other arrangement, you would not achieve a plane
of symmetry.
If we subtract the degrees of freedom used already from the total amount, 6 -(4+1)
= 1. We still have 1 degree of freedom, which must be used up by the ethyl. We had
narrowed down that signal to either an ether or ester. An ester uses 1 degree of
freedom, while an ether doesnt, meaning the signal at 4.30 most likely
represents an ester. Also looking at the molecular formula, 2 oxygens are used
for the carboxylic acid, and 2 are used for the ester, perfectly using up all of the
oxygens, while an ether would only use 1 oxygen, leaving an extra out.
So after all of that we know the following:
A benzene ring with a carboxylic acid and an ester with a ethyl substituent attached
to the benzene ring in a 1,4 fashion.
Piecing all of that together, we can draw the following

This matches the 6 degrees of freedom, and the molecular formula, the splitting
pattern, the number of hydrogens, and the shift range, and is in fact the structure
for the NMR.