EXPT.

9 DETERMINATION OF THE STRUCTURE

OF AN ORGANIC COMPOUND USING UV,
IR, NMR AND MASS SPECTRA
Structure
9.1 Introduction
Objectives
9.2 Principle
9.3 Requirements
9.4 Strategy for the Structure Elucidation of the Organic Compounds by Combined
Use of UV, IR, NMR and Mass Spectral Data.
Suggested Guidelines for Arriving at the Structure of Organic Compounds
9.5 Practice problems
9.6 Problems for the session
9.7 Solution to practice problems

9.1 INTRODUCTION
In the previous two experiments you have learnt about the applications of IR and NMR
spectroscopy respectively in the determination of functional groups in an organic
molecule. In this experiment you would learn about the determination of the structure of
simple organic molecules using UV, IR, NMR and Mass spectral data. You have learnt
about these spectroscopic methods and the structural information from them in the
MCH-003 course. In addition, you have embarked on the strategies for the
interpretation of the IR and NMR spectra to obtain the structural information in the
previous two experiments. You would recall from these that no spectroscopic method
can give all the information about the analyte being studied; however, these can provide
significant inroads into the structural details.

In this experiment we would first recall and reproduce the essential information from
the relevant units of the MCH-003 course and the Experiments 7 and 8 of this course
for the structural elucidation of organic molecules. This will be followed by a suggested
strategy and its application in solving the structural problems using the data from varied
spectra. You would be required to determine the structure of a few organic compounds
on the basis of the provided sets of spectra. Once equipped with the necessary
interpretative skills, you can sharpen your skills by interpreting as many spectra as
possible to attain a kind of mastery.

Objectives
After studying the contents of this experiment and solving the sample problems, you
should be able to:

• outline the salient features of different spectrometric methods,

• identify the presence of different functional groups and other structural features in
an organic compound on the basis of the IR, Mass and NMR spectra,

• formulate different tentative structures of the organic compound on the basis of

the above, and

• establish the unequivocal structure of the organic compound whose spectra have
been provided.

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Spectroscopic Methods
Lab 9.2 PRINCIPLE
In order to determine the structure of organic molecules on the basis of their spectra we
need to use all the structural information available in the spectra. The obvious first step
in this direction would be to dig out the same from the different spectra. You have
learnt about the structural information available in different types of spectra and the
strategy to obtain that from the spectra in Unit 14 of MCH-003 course and the
Experiments 7 and 8 of this course. Let us collate all this here, for a quick reference for
determining the structures of organic compounds from their spectra.

UV spectrum
An absorption in the UV-VIS region of the spectrum, i.e., the UV-VIS spectrum of a
molecule indicates the presence of certain functional groups that have characteristic
n → π *, π → π * transitions. The λ max and the intensity of the absorption bands are
indicative of the extent of conjugation in the molecule; larger the wavelength, greater
the conjugation. The spectrum itself does not provide much details of the structure of
the molecule. However, these transitions observed in this are so characteristic that the
absence of a UV-VIS spectrum for a molecule eliminates the presence of a number of
functional groups in the molecule. For example, an intense signal around 210 nm is
indicative of an α, β - unsaturated ketone, a diene or a polyene. Similarly two bands of
medium intensity with absorption maximum above 200 nm are suggestive of aromatic
ring.

IR spectrum
You have learnt about the theory of IR spectroscopy in the Unit 3 of MCH-003 course
and the application of the same in the determination of functional groups of organic
compounds in the experiment number 7 of this course. Let us recall the strategy of
using the IR spectral data for structural elucidation of organic compounds.

Important A. Determine the nature of carbon skeleton (aliphatic / aromatic)

3
sp C-H stretching : i) C–H stretching : The =C–H stretch in aromatics is observed at
2850 to 3000 cm-1 3100-3000 cm-1 whereas the –C–H stretching frequencies for saturated
2
sp C-H stretching :
aliphatic hydrocarbons is below 3000 cm-1.
above 3000 cm-1
sp C-H stretching :
~ 3300 cm-1.
ii) C–C ring stretching vibrations: The aromatic hydrocarbons show C-C
ring stretching vibrations in the regions 1600-1585 cm-1 and
1500-1400 cm-1

iii) Out of plane C–H bending vibrations: These are observed in the region
900-675 cm-1 and provide information about the substitution pattern of
aromatic compounds.

Thus, a weak absorption in the region 3080-3030 cm-1 accompanied by medium

absorption in the ring vibrations region indicates the presence of an aromatic ring.
A signal around 1605 cm-1 is quite a good indicator of an aromatic molecule;
occasionally it splits into a doublet. The out of plane bending vibrations are also
very significant. A lack of strong absorption band in the 900-650 cm-1 region
generally indicates a non aromatic structure.

B. Look for the characteristic frequencies of different functional groups.

a) Molecules containing only C and H i.e., hydrocarbons

Look for C–H stretching whether it is in the region 3000–2850 cm-1 or
above 3000 cm-1? The absorption above 3000 cm-1 indicates a double or a
triple bond. The following are other important signals to look for in a

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 hydrocarbon to ascertain its nature.
i) The C=C bond usually gives rise to a moderate band in the region
1680-1640 cm-1.
ii) The –C≡C– stretch appears as a weak band from 2260-2100 cm-1.
iii) The bending vibrations of the =C–H group are observed in the 1000-
650 cm-1 region.
iv) The terminal –C≡C– H stretch is observed as a strong, narrow band
in the range 3330-3270 cm-1.
v) The –C≡C– H bending vibration is observed in 700-600 cm-1 range.
vi) If a band observed at 1380 cm-1 happens to be a doublet, it may be
due to the presence of more than one methyl group on the same
carbon atom.

b) Molecules containing C, H and O or N

Look for a strong absorption in the region, 1820-1660 cm-1 for a C=O
group.

If carbonyl group is present, then we have a number of possibilities; look

for the following

i) Two weak absorptions near 2850 and 2750 cm–1 on the lower wave
number side of the CH absorptions.
These are due to O=C–H stretching vibrations. The band near
2830 cm-1 usually overlaps with other C–H stretching vibration bands
however, the presence of a moderate band near 2720 cm-1 is very
likely to be helpful in determining whether or not a compound is an
aldehyde. It often appears as a shoulder-type peak.
ii) Broad band in the region 3300-2500 cm-1, centred at about 3000 cm-1.
This arises due to the stretching vibration of O–H group of
carboxylic acids. The broad nature of the band is due to the fact that
carboxylic acids usually exist as hydrogen-bonded dimers.
iii) Two or more strong absorption bands in the region 1300-1000 cm-1
These are due to the C–O stretching vibrations in esters.
iv) If the above three are absent then the molecule could be a ketone

Similarly, if C=O absorption is absent, look for the following

i) The N–H stretching vibrations of amines in the region 3300-

3000 cm-1
These are observed to be weaker and sharper than those observed for
the O–H stretching vibrations of alcohols which appearing in the
same region. The presence of two bands is suggestive of a primary
amine whereas a single band is indicative of a secondary amine.
ii) The corresponding C–N stretching vibrations of aliphatic amines are
observed as medium or weak bands in the region 1250-1020 cm-1.
The same for aromatic amines are usually observed as strong band in
the 1335-1250 cm-1.

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Spectroscopic Methods iii) Nitrile (– C≡N) shows a medium, sharp absorption band in the range
Lab 2260-2220 cm-1. The isomeric isocyanate’s strong bands are
observed in the range 2275-2240 cm-1.

c) Molecules containing C, H, O and N

For the molecules having this elemental composition, two most common
functional groups are amide and nitro. Their absorptions can be looked for
in the following regions.
i) Amide: The amides show a characteristic absorption band for the
carbonyl group in the region, 1700-1640 cm-1. It is also referred to as
the Amide I band.
In addition, the N–H stretching vibrations are observed in the 3500-
3100 cm-1. The primary amides show two N–H stretching bands
whereas the secondary amides give rise to only one such band.
ii) Nitro: In nitroalkanes the N–O stretching vibrations occur in the
range of 1550 - 1365 cm-1; the band at higher value being the
stronger of the two. On the other hand for the nitro group attached to
an aromatic ring, the N–O stretching bands are observed in the ranges
of 1550-1475 cm-1 and 1360-1290 cm-1.

NMR Spectrum
Chemical You would recall from Unit 12 of MCH-003 course and Experiment 8 that the
Structure shift following features of NMR spectra and the structural information available from them
(ppm) play important role in the structure elucidation of an organic molecule.
RCH3 0.8 - 1.2
R2CH2 1.1 - 1.5 i) The number of different signals in the 1H-NMR spectrum indicates about the
different types of protons present in the molecule.
R3CH ~1.5
ArCH3 2.2 - 2.5 ii) The position of the signals i.e. their chemical shift values, tells about the
R2NCH3 2.2 - 2.6 electronic environment of a particular proton. The chemical shifts of different
R2CHOR 3.2 - 4.3
types of protons are given in Fig. 9.1.
R2CHCl 3.5 - 3.7
RC(=O)CHR2 2.0 - 2.7
RCHCR=CR2 ~1.7
RC=CH 4.9 - 5.9
ArH 6.0 - 8.0
RC(=O)H 9.4 - 10.4
RCCH 2.3 - 2.9
R2NH 2-4
ROH 1-6
ArOH 6-8
RCO2H 10 - 12

Fig. 9.1: Range of chemical shift values for different types of protons
iii) The area under the peaks obtained from the integrals for the signals of various
types of protons provides information about the ratio of the numbers of different
types of protons present in a molecule.
iv) The spin-spin splitting pattern of a particular signal gives information about the
number of neighbouring protons present around the given type of protons. The
splitting pattern in accordance with the n+1 rule helps in identifying important
groupings.

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Some characteristic features to look for in the NMR spectrum
• A combination of two proton quartet and a three proton triplet are suggestive of
an ethyl group; similarly, a six proton doublet and a one proton septet (or
multiplet) is characteristic of an isopropyl group.
• A signal in the range of 9-10 ppm is characteristic of an aldehyde group as no
other type of hydrogen appears in this region; similarly, a signal in the range of
11-12 ppm is characteristic of a carboxylic acid; the hydrogen is highly
deshielded by the oxygen and is acidic in nature.
• The broadened singles in the spectrum indicate towards the presence of –OH
or –NH protons.
• The absorptions in the range of 7 − 8 ppm suggest the presence of an aromatic
ring; benzene absorbs at 7.27 ppm. The aromatic absorptions are farther
downfield than δ = 7.27 , indicate the presence of electron-withdrawing
substituents.
• The absorptions in the region of δ = 2.1 to δ = 2.5 are indicative of the protons
adjacent to a carbonyl group or an aromatic ring.

Mass spectrum
+
i) The m/z value of the molecular ion, M • gives the molecular mass and can also
be used for generating the molecular formula (subsec. 13.4.1).
+ +
ii) The relative intensities of [M + 1] • and [M + 2] • peaks can be related to the
number and nature of hetero atoms present in a molecule. You would recall from
Unit 13 that a typical pattern of M + 1 and M + 2 peaks is observed if a chlorine
or bromine atom is present in the molecule.
iii) The odd molecular mass is indicative of the presence of a nitrogen atom in the
molecule. However, this has to be further confirmed by other means or by
analysing the fragmentation patterns for the typical nitrogen containing functional
groups.
iv) The characteristic peaks arising from typical fragmentation patterns of various
classes of functional groups such as α ‒ cleavage, loss of small molecules such as
H2O, C2H4, etc. are quite useful.
v) Certain peaks which may be attributed to the rearrangement of the molecular ion
or its fragments ions also give significant structural leads.
Table 13.2 of Unit 13 of MCH-003 course containing commonly lost fragments and
stable fragment ions observed in the mass spectrum is being reproduced here so as to
facilitate you in the interpretation of the mass spectra of the examples being taken up in
the next section.
Commonly lost fragments
Fragment lost Peak obtained Fragment lost Peak obtained
. +. . OCH +
CH3 M 15 3 M . - 31

+ . +
M.
.
OH 17 Cl M. - 35
.
. +
CN M. 26
CH3C O M +. - 43
CH2 + +
M.
H2C . . - 45
28 OCH2CH3 M

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Spectroscopic Methods . CH2CH3 + +
Lab M. 29 . M . - 91
CH2

Common stable ions

m/z values Ion
m/z = 43 +
CH3 C O
.
m/z = 91 . +
+
CH2

O.
+
m/z = M . - 1 +
R C O
R CH

Having learnt about the information available from different types of spectral data, we
can now take up how to use it to arrive at the structure of a given compound.

9.3 REQUIREMENTS
The main objective of this experiment is to highlight the structure-spectrum
relationships of organic molecules and interpret the spectra of some simple organic
molecules. We intend to inculcate elementary interpretative skills in you so that you can
take up the interpretation of the different spectra of some simple molecules to determine
their structure. Accordingly, we need the spectra of some simple molecules to be used
as examples and some others to be used as study problems.

9.4 STRATEGY FOR THE STRUCTURE ELUCIDATION

OF THE ORGANIC COMPOUNDS BY COMBINED
USE OF UV, IR, NMR AND MASS SPECTRAL DATA
You would have realised from your study of the MCH-003 course on Spectroscopic
Methods of Analysis and the previous two experiments of this course that there is no
unique methodology to decipher the structural aspects of the molecule on the basis of
their spectra. You have learnt about interpreting the IR and NMR spectra in the
previous two experiments while in Unit 14 of the MCH-003 course you learnt about
using Mass spectrum. You are advised to have a relook at the above referred content
though some part of that will be reproduced in the next section.

Based on the experience in solving structural problems, we suggest a comprehensive

scheme / strategy of arriving at the structure of the molecule from its various spectra.
Let us reiterate that this is not a unique approach, you may follow any other strategy
available elsewhere with an objective of being able to decipher the structure of the
organic molecule from its spectral data.

9.4.1 Suggested Guidelines for Arriving at the Structure of Organic Compounds

When you first look at a spectrum, consider the major features before getting down to
the minor details. The following are a few of the important characteristics you might
look for:

1. If the molecular formula is known, compute the index of hydrogen deficiency

(IHD). This would help ascertain the number of elements of unsaturation in the
compound. This in turn suggest about the presence of rings, double bonds, or
triple bonds.

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2. Examine each spectrum (IR, mass spectrum, 1H NMR) in turn for obvious
structural elements:
1. Examine the IR spectrum for the presence or absence of groups with
diagnostic absorption bands e.g. carbonyl groups, hydroxyl groups, NH
groups, C≡C or C≡N, etc. using the suggestions given in Experiment 7 and
reproduced in section 9.3.
2. Explore the mass spectrum for typical fragments e.g. PhCH2 –, CH3CO–
CH3 –, etc. look for the characteristic fragmentation pattern as detailed in
Unit 13 of the MCH-003 course; these are reproduced in section 9.3 for
your reference. Do remember that the mass spectra can provide clues about
the presence of halogen atoms also.
3. The number of signals in the 1H-NMR spectrum indicates about the
different types while their position indicates about the electronic
environment of different protons in the molecule. Analyse the NMR
spectrum for the characteristic spectral clues for the characteristic
groupings like – C2H5, – CH (CH3)2, aromatic rings, acid/ aldehyde groups
etc. as detailed in Experiment 8 and reproduced in section 9.

3. Write down all structural elements you have identified. You may arrange them as
monofunctional (i.e. – CH3, – C2H5 , – C≡N, PhCH2 –, CH3CO –, – NO2, etc.)
bifunctional (e.g. – CO –, – CH2 –, – C≡C–, – COO – , etc.), or trifunctional (e.g.
>CH–, >N – etc.). Add up the atoms of all the identified structural elements and
compare it with the molecular formula to determine the unaccounted component
of the molecular formula. The nature of the undetermined structural elements
may be quite apparent.

4. Try to assemble the structural elements to workout a tentative structure of the

molecule. You may have more than one tentative structures assembled from the
fragments.

5. Revisit the spectra again to see that whether they (especially the NMR and Mass
spectra) are accounted for by which of the proposed tentative structure. You may
need to relook into some of your earlier assignments at this stage.

These guidelines are suggestive only and seem to facilitate making educated guesses
about the major structural features of a compound from its different spectra. The
ingenuity lies in connecting the pieces of structural information to arrive at the structure
of the molecule. The only way to acquire expertise in obtaining the structures of organic
compounds from spectra is to practice, practice, more practice and even more practice.

9.5 PRACTICE PROBLEMS

Having recalled what you had learnt earlier about the information available from
different types of spectra and having learnt the proposed strategy for interpreting the
spectra to decipher the structure of simple organic compounds you have the necessary
tools in your toolkit to unravel the structure- spectral interrelationships. You are being
provided with the Mass IR and NMR spectra of some known organic compounds so
that you can test the proposed strategy or may be devise one of your own for
determining the structure of an organic compound from its spectra. The answers to
these are provided in section 9.7. You are required to solve these practice problems and
then verify your answers. Refrain from looking into the answers before solving the
problem.

Practice problem 1: The following are the Mass, IR and NMR spectra for a simple
organic compound having a molecular formula, C4H8O. Determine its structure.

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Spectroscopic Methods
Lab

Practice problem 2: The following are the Mass, IR and NMR spectra for a simple
compound having a molecular formula C5H10O2. Determine its structure.

74
Practice problem 3: The following are the Mass, IR and NMR spectra for a simple
compound having a molecular formula C3H8O. Determine its structure.

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Spectroscopic Methods
Lab

Practice problem 4: The following are the Mass, IR and NMR spectra for a simple
compound having a molecular formula C9H10O. Determine its structure.

76
Practice problem 5: The following are the Mass, IR and NMR spectra for a simple
compound having a molecular formula C3H5N.. Determine its structure.

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Spectroscopic Methods
Lab

9.6 PROBLEMS FOR THE SESSION

We are sure that on the basis of the suggested strategy and the expertise you had
acquired in interpreting the IR and NMR spectra in Experiments 7 and 8 you have been
able to solve the problems raised in the previous section. If not (for any problem) then
you would have convinced yourself that the given spectra are consistent with the
structure of the organic compound given in section 9.7.

We hope that you are now equipped to interpret the spectra of simple organic molecules
to determine their structure. You are provided with four sets of spectra for
interpretation. You may take the spectra in any sequence and try to interpret on the
basis of the knowledge gained. (Your counselor may provide you additional sets of
spectra of simple organic molecules to assess your understanding.) You must pin up the
spectra in the record book and submit your observations and results to your counsellor
for evaluation.

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Session problem 1

Session problem 2

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Spectroscopic Methods
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Session problem 3

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Session problem 4

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Spectroscopic Methods
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Session problem 5

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9.7 SOLUTION TO PRACTICE PROBLEMS
Practice problem 1: Butanone-2
Practice problem 2: Ethylpropionate
Practice problem 3: 1-propanol
Practice problem 4: Propiophenone
Practice problem 5: Propane nitrile

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