Week 7 Structure Determination using Nuclear Magnetic

Resonance Spectroscopy

7.1 Introduction
7.2 Predicting the 1H spectra using molecular structure
7.3 Predicting the molecular structure using 1H spectrum
7.4 Summary

Learning Outcomes
After completing this unit, you should be able to:

 Predict the number of proton NMR signals expected from a compound given its
structure.
 Predict the splitting pattern in the proton NMR spectrum of a compound given its
structure.
 Assign peaks in an NMR spectrum to specific protons in a compound with the aid of a
chart of chemical shifts from 1H NMR.
 Interpret integration of NMR spectra.
 Use NMR spectra to determine the structure of compounds, given a molecular
formula.

Recommended reading

1. McMurry, J.; Organic Chemistry

8th Edition, Chapter 13, sections 13.1-13.3, 13.8-13.13
6th Edition, Chapter 13, sections 13.1-13.3, 13.8-13.13

2. Solomons, T. W. G.; Organic Chemistry

6th Edition, Chapter 14, sections 14.4-14.12

Why study this topic?/ Importance of the topic

Read:
1. McMurry, J.; Organic Chemistry
8th Edition, Chapter 13, A Deeper Look
6th Edition, Chapter 13, Chemistry@Works
7.1 Introduction

NMR spectroscopy is a great tool for determining structures of organic compounds. As you
know 1H spectra have three features-chemical shift (the position of the signal), signal
intensity, and the multiplicity each providing useful information in determining the
structure. We will see later, how we will use each information to determine the structure.
Most of you really get to understand the concept of 1H NMR spectroscopy.

In this unit we will see how we can use these features together to assign structures from 1H
spectra. Also how we can predict the possible 1H spectra given the molecular structure. We
will take the following problem solving approaches.

7.2 Predicting the 1H spectra using molecular structure

We will begin with the following approach:

1. note if the molecule has a symmetry (this will decrease the number of signals)
2. determine how many signals are possible in the given molecule (we will look for
equivalent hydrogens)
3. determine the multiplicity of each signal cluster (count the number of hydrogen atoms
attached to the neighbouring carbon atom)
4. calculate the possible chemical shifts using the table below taking into account the
positions of electronegative atoms in the molecule)
Let us predict the possible 1H spectra of the following molecules.
 CH CH CH2Br
3 2
Example1:
No. of signals
No line of symmetry
But there are:
2 identical H’s on C1 which will give 1 signal
2 identical H’s on C2 which will give 1 signal
3 identical H’s on C3 which will give 1 signal
There will be 3 signals on the 1H spectra

The possible chemical shifts will be: H on C1= 1.2+2.18

2H’s on C1 will have the greatest deshielding due to Predicted H on C1=3.38
bromine
Chemical shift of H on C1:
Base chemical shift =1.2 H on C2= 1.2+0.6
α-Br = 2.18 (table 7.1) Predicted H on C2=1.8

2H’s on C2 will have the less deshielding as bromine is on C1 Predicted H on C3=1.2

Chemical shift of H on C2:
Base chemical shift =1.2
β-Br = 0.6 (table 7.1)

3H’s on C3 will have the little or no effect

Chemical shift of H on C2:
Base chemical shift =1.2
Multiplicities
C1 has 2 H which will give 1 signal and 2H on the neighbour
Splitting this signal into 1+2=3 (triplet, t)
C2 has 2H which will give 1 signal and 3H on one neighbour,
2H on another neighbour
Splitting will be 1+2+3=6 (multiplet, m)
C2 has 3 H which will give 1 signal and 2H on the neighbour
splitting =1+2=3 (triplet, t).

Predicted 1H NMR of bromopropane will be:

 O
CH CCH CH
3 2 3
Example 2:
No. of signals
No line of symmetry
But there are:
3 identical H’s on C1 which will give 1 signal
No H’s on C2, therefore no signal
2 identical H’s on C3 which will give 1 signal
3 identical H’s on C4 which will give 1 signal
There will be 3 signals on the 1H spectra
The possible chemical shifts will be:
2H’s on C1 will have the deshielding due to carbonyl group H on C1= 0.9+1.2
Chemical shift of H on C1: Predicted H on C1=2.1
Base chemical shift =0.9
α-CO = 1.2 (table 7.1)

2H’s on C3 will have deshielding due to carbonyl group on H on C3= 1.2+1.2

C2 Predicted H on C3=2.4
Chemical shift of H on C2:
Base chemical shift =1.2
α-CO = 1.2 (table 7.1)
Predicted H on
C4=0.9+0.18
3H’s on C4 will have the little or no effect
=1.08
Chemical shift of H on C4:
Base chemical shift =0.9
β-CO=0.18
Multiplicities
C1 has 3H which will give 1 signal and has none H’s on the
neighbour. Splitting will be 1+0=1 (singlet, s)
C3 has 2H which will give 1 signal and 3H on the neighbour
Splitting will be 1+3=4 (quartet, q)
C4 has 3H which will give 1 signal and 2H on the neighbour
splitting =1+2=3 (triplet, t).

Predicted 1H NMR will be:

 O
CH CH COCH CH
3 2 2 3
Example 3:
No. of signals
No line of symmetry. But there are:
3 identical H’s on C1 which will give 1 signal
2 identical H’s on C2 which will give 1 signal
No H’s on C3, therefore no signal
2 identical H’s on C4 which will give 1 signal
3 identical H’s on C5 which will give 1 signal
There will be 4 signals on the 1H spectra
The possible chemical shifts will be:
3H’s on C1 will have the deshielding due to carbonyl group H on C1=0.9+0.18=1.08
Chemical shift of H on C1:
Base chemical shift =0.9; β-CO = 0.38 (table 7.1)

2H’s on C2 will have deshielding due to CO group on C3 H on C2= 1.2+2.88

Chemical shift of H on C2: Predicted H on C2=4.08
Base chemical shift =1.2; α-CO = 2.88 (table 7.1)

2H’s on C4 will have deshielding due to O which is EN atom H on C4= 1.2+1.05

Chemical shift of H on C4: Predicted H on C4=2.25
Base chemical shift =1.2; α-O = 1.05 (table 7.1)
H on C5: 0.9+0.38
3H’s on C4 will have the little or no effect
Predicted H on C5=1.28
Chemical shift of H on C4:
Base chemical shift =0.9; β-CO=0.18
Multiplicities
C1 has 3H which will give 1 signal and has 2H’s on the
neighbour. Splitting will be 1+2=3 (triplet, t)
C2 has 2H which will give 1 signal and has 2H’s on the
neighbour. Splitting will be 1+2=3 (triplet, t)
C4 has 2H which will give 1 signal and 3H on the neighbour
Splitting will be 1+3=4 (quartet, q)
C5 has 3H which will give 1 signal and 2H on the neighbour
splitting =1+2=3 (triplet, t).
7.3 Predicting the molecular structure using 1H spectrum

Part 1: Begin with a general examination of the spectrum:

1. Determine how many signals are there in the 1H spectrum.

2. Note the chemical shifts of each signal.
3. Determine how many 1H nuclei are present in each signal (look at the integration).
4. Determine the multiplicity of each signal (count the number of peaks)
5. Use the molecular formula to subtract groups that you have identified and check
needs to identify).

Part 2: Now proceed to the interpretation of the spectrum:

6. For each peak, you need to match the number of 1H nuclei and its multiplicity with a
corresponding peak and combine it to the groups.
7. Record each group you recognize (this will give you partial marks).
8. When you have assigned all 1H groups that you recognize, add their formulas up and
compare with the molecular formula; the difference will be a group or groups that
you have not identified as yet or cannot see in the 1H spectrum.
9. Enter the “difference” and combine all fragments together.

Part 3: Check your work:

10. Make sure that you have accounted for all signals and for every atom of the
molecular structure and that your combined structure satisfies all chemical shifts.
Let us determine the structure of a molecule using a given 1H spectrum. Let us begin by
looking at a simple compounds first and then we will look at some complex compounds.

Example 1: The molecular formula and 1H spectrum of the compound C 4H6Cl2 is given below.
Determine the structure of the molecule.

Solution:
The molecular formula of compound is C4H6Cl2 and the 1H spectrum has 3 signals. Since
there are 4 carbon atoms in the molecule and 3 signals means that there must be a C atom
without any H attached.

To interpret individual peaks, it is best to start at one end of the spectra and present it in a
table format. (You may pick the signal in low field or high, left or right.)

Chemical shift (ppm) Multiplicity H neighbours Integration Structure of fragment

9.7 singlet n=0 1H
n+1=1 no H on the
means n = neighbour
0
At low field (left) the spectrum has a singlet integrating for 1 H at 9.7 ppm; this chemical
shift without doubt indicates an aldehyde. Because this signal is a singlet (n + 1 = 1; n = 0),
which means that there are no 1H nuclei on the adjacent carbon.

Now let us go to high field (on the right): there is a triplet integrating for 3 H at 0.9 ppm; 3 H
at 0.9ppm is almost always a methyl group. The signal is a triplet (n + 1 = 3); therefore, the
methyl group must have 2 H neighbours; which must be a CH 2 group. The CH2 signal is a
quartet (n +1 = 4), so it must have (n =) 3 H neighbours; that can only be the CH 3 group.

Note:
 We should know that there cannot be any H neighbour on the other side of the CH 2
group.
 The combination of a “triplet, 3 H” with a “quartet, 2 H” is ALWAYS a C2H5 group.

Chemical shift (ppm) Multiplicity H neighbours Integration Structure of fragment

9.7 singlet n=0 1H
n+1=1 no H on the (CH)
means n = neighbour C
0
2.1 quartet n=3 2H
n+1=4 3H on the (CH2 circled)
means n = neighbour C
3
0.9 triplet n=2 3H
n+1=3 2H on the (CH3 circled)
means n = neighbour C
2

So far we have no information how the two groups are connected.

Let us go back to the molecular formula, C4H6Cl2:

You subtract the two fragments, CHO and C2H5 (C4H6Cl2 – CHO – C2H5 = CCl2). We are left with
a dichloromethylene unit. So the three fragments are as:
There is only one way how the three units can be connected into a molecule.

Example 2: The molecular formula and 1H spectral data of the compound C3H7Br is given
below. Determine the structure and name of the molecule.

1
H-NMR (ppm) Spectral data:
3.39 ppm (triplet, integral=1.0)
1.87 ppm (sextet, integral=1.0)
1.03 ppm (triplet, integral=1.5)

Solution:

The molecular formula of the compound is C3H7Br and the 1H spectrum has 3 signals. There
are 3 carbon atoms in the molecule and there are 3 signals means that there is every C atom
that has H atoms attached.
In the molecular formula, there are 7 H’s in total and the integration only accounts for 3.5
H’s. So we need to multiply each integral by 2: [2X (1:1:1.5)]=2:2:3. This will give a total of 7
H’s.

The 1H-NMR (ppm) Spectral data now will be:

3.39 ppm (triplet, integration=2)
1.87 ppm (sextet, integration =2)
1.03 ppm (triplet, integration =3)

To interpret individual peaks, it is best to start at one end of the spectra and present it in a
table format. (You will pick the signal in high field, right.)

Chemical shift (ppm) Multiplicity H neighbours Integration Structure of fragment

1.03 triplet n=2 3H
n+1=3 2H on the (CH3 circled)
means n = neighbour
2

At high field (right) the spectral data has a triplet integrating for 2 H at 1.03 ppm; this
chemical shift around this region with integration of 3 H is almost always a methyl group.
The signal is a triplet (n + 1 = 3); therefore, the methyl group must have 2 H neighbours;
which means that there must be a CH2 group.
There are two CH2 signals. One will splits into a sextet and the other splits into a triplet. Let
us look at the CH2 signal which is a sextet (n +1 = 6), so it must have (n =5) 5 H neighbours.
This is an indicative of CH3-CH2-CH2- group.

Chemical shift (ppm) Multiplicity H neighbours Integration Structure of fragment

1.03 triplet n=2 3H
n+1=3 2H on the
means n = neighbour
2
1.87 sextet n=5 2H
n+1=6 5H on the (CH2 circled)
means n = neighbours C
5 ie 3H as CH3
and 2H as
CH2
3.39 triplet n=2 2H
n+1=3 2H on the (CH2 circled)
means n = neighbour C
2
So far we have the connection of all 3 carbon atoms. Let us go back to the molecular
formula, C3H7Br: We have accounted for 3 carbon atoms, 7 hydrogen atoms. We are left
with a bromine atom.
Thus, the structure of the molecule is CH3-CH2-CH2-Br and the name is bromopropane.
Note: The H’s attached to the Br is at 3.39 ppm (lower field) as Br is electronegative atom.

Example 3: The molecular formula and 1H spectral data of the compound C5H10O is given
below. Determine the structure and name of the molecule.

Solution:

The molecular formula of the compound is C5H10O and the 1H spectrum has 4 signals. There
are 5 carbon atoms in the molecule and there are 4 signals means that there is one C atom
that has no H atoms attached.

In the molecular formula, there are 10 H’s in total. Let us look at the integration line to
determine the identical H’s. This time we will have to measure the integration line. Let’s
measure the integration line first and put the spectral data.

The 1H-NMR (ppm) Spectral data now will be:

2.4 ppm (triplet, integration line=7mm)
2.2 ppm (singlet, integration line=11mm)
1.6 ppm (sextet, integration line =7mm)
0.9 ppm (triplet, integration line =11mm)
The integration line shows: 7:11:7:11. To obtain the ratio of peaks, we will divide all
numbers by 7. This will give a simplified ratio of 1: 1.6: 1:1.6. Since we have 1.6 H atom
ratios which is not possible plus the total H atoms in the simplified ratio comes to 5.2H’s
which is when rounded off gives 5H atoms. This is half of the total number of H atoms listed
in the formula. So let us round off the simplified ratios and multiply by 2 ie 2 X (1: 1.5: 1:1.5.)
and we will get 2:3:2:3 for each signal. This will give a total of 10 H’s.

So now we have:
The 1H-NMR (ppm) Spectral data now will be:
2.4 ppm (triplet, 2H)
2.2 ppm (singlet, 3H)
1.6 ppm (sextet, 2H)
0.9 ppm (triplet, 3H)

To interpret individual peaks, it is best to start at one end of the spectra and present it in a
table format. (You will pick the signal in high field, right.)

Chemical shift (ppm) Multiplicity H neighbours Integration Structure of fragment

0.9 triplet n=2 3H
n+1=3 2H on the (CH3 circled)
means n = neighbour
2

At high field (right) the spectral data has a triplet integrating for 3 H at 0.9 ppm; this
chemical shift around this region with integration of 3 H is almost always a methyl group.
The signal is a triplet (n + 1 = 3); therefore, the methyl group must have 2 H neighbours;
which means that there must be a CH2 group.

The second signal which has a sextet integrating for 2 H at 1.6 ppm; this chemical shift
around this region with integration of 2 H means that there is a CH 2 signal. However, it
means that this signal has 5 H atoms in a neighbouring carbon. We know that there is a CH 3,
which accounts for 3H’s in the neighbour. To have 5 H’s in a neighbour, this CH 2 needs to
have another neighbour that will have 2H atoms ie another CH2.
Let us check the spectra again: There is another signal at 2.4 ppm which is a triplet and
integrates for 2H’s. This means that this a CH 2 which must be the other neighbour for CH 2.
So know we know that there are 2 x CH 2 groups bonded together. One will splits into a
sextet and the other splits into a triplet. Let us look at the CH 2 signal which is a sextet (n +1 =
6), so it must have (n =5) 5 H neighbours. This is an indicative of CH 3-CH2-CH2- group.

Chemical shift (ppm) Multiplicity H neighbours Integration Structure of fragment

0.9 triplet n=2 3H
n+1=3 2H on the
means n = neighbour
2
1.6 sextet n=5 2H
n+1=6 5H on the (CH2 circled)
means n = neighbours C
5 ie 3H as CH3
and 2H as
CH2
2.4 triplet n=2 2H
n+1=3 2H on the (CH2 circled)
means n = neighbour C
2

Now let us look at the signal at 2.2 ppm which is a singlet and integrates for 3H. This means
that it is a CH3 group with zero H atoms (n+1=1) in the neighbour. However, a CH 3 group
normally appears around 0.9 ppm. This signal appearing downfield means that it must be
attached to an electronegative atom or electron withdrawing group.

Note: The signal at 2.4 ppm which is a CH 2 must also be attached to an electronegative atom
or electron withdrawing group as a CH2 group normally should appear around 1.2ppm.

Chemical shift (ppm) Multiplicity H neighbours Integration Structure of fragment

0.9 triplet n=2 3H
n+1=3 2H on the
means n = neighbour
2
 1.6 sextet n=5 2H
n+1=6 5H on the (CH2 circled)
means n = neighbours C
5 ie 3H as CH3
and 2H as
CH2
2.2 singlet n=0 3H
n+1=1 no H’s on the (CH3)
means n = neighbour C
0
2.4 triplet n=2 2H
n+1=3 2H on the (CH2 circled)
means n = neighbour C
2
Missing atoms are C and O which can be a carbonyl group C=O

So far we have the following fragments:

1. We have the connection of all 3 carbon atoms ie CH3-CH2-CH2-
2. We have a CH3- not connect to the propyl group.

Let us go back to the molecular formula, C5H10O r: We have accounted for 4 carbon atoms,
10 hydrogen atoms. We are now left with a carbon and an oxygen atom. The two fragment
must be connected to a carbon atom which is connected to an oxygen atom. Since each
atom has the required number of bonds, the C and O must form a C=O carbonyl group.

Thus, the name is 2-pentanone and the structure of the molecule is:

7.4 Summary

 The number of proton NMR signals can be predicted of a given compound using the
structural arrangement of the atoms.
 The splitting pattern in the proton NMR spectrum of a given compound is based on
the number of hydrogen atoms in the neighbouring carbon atoms.
 Chemical shifts of the peaks in an NMR spectrum can be predicted using a chart of
chemical shifts from 1H NMR and the type of atoms attached to the carbon atoms
bearing the hydrogen nuclei.
 We can predict the integration or equivalent hydrogen atoms based on the
integration line or the given integration in a NMR spectra.
  The structure a compound given a molecular formula can be determined by the
chemical shifts, integration and the splitting patterns of the signals in a NMR spectra.

Activity:
You can follow the examples in this week’s readings to answer the 1H NMR problems given
(as a separate document). You MUST attempt all the questions to fully understand the
concepts of 1H NMR.