Q5(a).

A compound A, having molecular formula C3H6O, shows the following IR, H-NMR
and Mass spectra respectively . Deduce its structure.
Solution
There is no unique way of solving a problem of structure elucidation. What we need todo is
to pick up all the important information available from the spectra and thenintegrate them
to arrive at the structure. Sometime one or two spectra give enough cluesto the structure. In
such cases we suggest a tentative structure and check that whether it
supports the other data. Let us make a beginning.

IHD: We start with calculation of IHD.

 Number of hydrogen atoms 
IHD = Number of carbon atoms −  
 2 
 Number of halogen atoms   Number of nitrogen atoms 
−  +  + 1
 2   2 
Therefore, IHD=3‒6/2 = 0

The IHD of zero clearly shows that the molecule does not have any unsaturation or a
ring structure.

IR: A strong absorption around 1700 cm‒1 is indicative of a carbonyl group (>C = O);
this may account for the oxygen in the molecule.

NMR: The NMR spectrum provides two important bits of information as given below.

i) A single signal indicates that only one type of protons is present in the molecule
i.e., all the protons are equivalent.

ii) The chemical shift of δ = 2.2 indicates that the protons are slightly deshielded;
may be due to being in the neighbourhood of an anisotropic group (>C = O)

Mass: The mass spectrum shows prominent peaks at m/z 15, 43, 58. The M+ ion
appears at m/z 58 while the base peak is at m/z 43. The M+ peak is in accordance with
+
the molecular formula and the base peak (M‒15) is indicative of a stable C OCH 3 ion
 •
which is obtained by the loss of C H 3 radical from the molecular ion. Similarly the peak
•
at m/z =15 can be attributed to the loss of C OCH 3 (M‒ 43) from the molecular ion.

Thus, the fragmentation pattern in mass spectrum indicates presence of CH3 and
COCH3 groups.

On the basis of the above information i.e. the presence of >C = O group (from IR),
− COCH3 and – CH3 (from MS) we may propose the structure of the compound A to be
the following.
O

CH3 C CH3
Compound A

This structure also explains the equivalence of all the protons observed in 1H-NMR
spectrum. Thus, we can say that the compound A is acetone having the structural
formula as shown above.

Fig. 14.6: IR Spectrum of Compound B

64
 Structure Elucidation
by Integrated
Spectroscopic Methods

Fig. 14.7: 1H-NMR Spectrum of Compound B

Solution
IHD: Let us again start with the molecular formula and calculate its IHD, we get
 Number of hydrogen atoms 
IHD = Number of carbon atoms −  
 2 
 Number of halogen atoms   Number of nitrogen atoms 
− +  + 1
 2   2 
8
= 7−+1
2
= 7− 4 +1
= 4
The IHD of four suggests that the compound does contain a ring and/or double bonds.

NMR: The NMR spectrum is quite useful in this case and provides the following
information.
i) There are two types of protons
ii) The integration of the peaks shows that the number of the two types of
protons is in the ratio of 5:3.
iii) The signal at δ =7.2 indicates the presence of benzene ring.
iv) The other signal for three protons at (δ =2.2) can be attributed to a –CH3
group attached to a benzene ring.
=> the presence of benzene ring accounts for the IHD of 4 (a ring and three
double bonds)

IR: There are very important pieces of information available from the IR spectrum.
i) The bands in the region of 1400‒1600 cm‒1 point to the presence of a
benzene ring; the signal at 1605 cm‒1 is quite characteristic of the same.

65
Miscellaneous Methods ii) Two strong peaks near 690 cm‒1 and 750 cm‒1 indicate monosubstituted
benzene ring. These are due to out of plane bending of aromatic = C − H.
The overtones of bands are observed between 2000 ‒1667 cm‒1.
iii) The signal at about 3050 cm‒1 can be ascribed to sp2 C − H stretching,
while at about 2900 cm‒1 is due to sp3 C − H stretching.
Thus, the IR spectrum clearly points to a monosubstituted benzene.

Mass: The mass spectrum given in Fig. 14.5 shows the M+ peak at m/z 92 and the base
peak at m/z 91. Looking at the table we can say that this peak could be due to benzyl
carbocation, as shown in the following structure.
+
CH2

Benzyl carbocation
The spectral data evidences indicate that compound B to have the following structure
CH3

Toluene
And, hence the compound B is toluene.

Example 3
A compound C, having molecular formula C7H6O, exhibits the following spectra:

Fig. 14.8: Mass spectrum of compound C

66
 Structure Elucidation
by Integrated
Spectroscopic Methods

Fig. 14.9: IR spectrum of compound C

Fig. 14.10: 1H‒ NMR spectrum of compound C

Solution
To arrive at its structure, we start with the determination of IHD from its molecular
formula. We get,
6
IHD = 7 − + 1
2
= 7−3 + 1
=5

Again, there may be a possibility that the ring and/or the double or triple bonds may be
present in the structure of the molecule.

IR: Similar to the previous compound the IR spectrum, suggests for a monosubstituted
benzene.
i) The aromatic C = C stretch is observed between 1600 −1450 cm‒1.

67
Miscellaneous Methods ii) Two strong peaks near 690 cm‒1 and 750 cm‒1 are indicative of out of plane
= C − H bending for monosubstituted benzene.
iii) In addition, the strong signal at 1700 cm‒1 suggests for the carbonyl group.
iv) The doublet, between 2850 cm‒1 and 2750 cm‒1 is characteristic of C− H stretch
of aldehydes. This further qualifies the nature of carbonyl group.
Thus, an IHD of 4 out of 5 is accounted for by the presence of benzene unit (which
contains one ring and three double bonds) and the fifth by the carbonyl group.

Thus, you may see here that the IR spectrum has provided enough leads to suggest a
plausible structure. In the molecule, an aldehyde (−CHO) group is linked to the
monosubstituted benzene ring. Hence, the compound has the structure C6H5CHO. Let
us look into other spectra and see do they support the assignment.

NMR: The NMR spectrum also supports the proposed structure. Let us see the
available information.
i) The multiplet between δ 7.4 – 7.9 is suggestive of aromatic protons.
ii) The one proton signal at δ 9.8 is quite useful as it is suggestive of an aldehydic
proton.
The complex multiplet between δ 7.4 – 7.9 when resolved under high resolution shows
that there are three different types of aromatic protons and these are in the ratio of
2:1:2. The multiplet when observed at higher resolution (at 300 MHz) shows a doublet
(2H) and two triplets. The doublet at δ =7.5 is due to two ortho protons. The triplet due
to (1H) at ∼ δ 7.6 is due to para proton and the other triplet is due to 2 meta protons
appears at about δ 7.9. Thus, the 1H-NMR spectral data also supports that the
compound is benzaldehyde. Let us see what does the mass spectrum say.

Mass: The mass spectrum also supports the suggested structure. Let us analyse the
evidence.
i) The molecular ion gives an intense M+ peak at m/z = 106.
ii) An equally intense M – 1 peak at m/z 105 is suggestive of the loss of one
hydrogen via the α -cleavage process – a very favourable fragmentation
mechanism.
iii) The characteristic peak at m/z 77 can be due to the loss of – CHO to
give C 6 H 5+ ion.

iv) A further loss of HC = CH from C 6 H 5+ ion yields C 4 H 3+ ion; the peak for which
is observed at m/z 51 in the mass spectrum.
Thus, all the above spectral data confirm that the compound C is benzaldehyde and it
has the following structure.
CHO

Benzaldehyde
Example 4
A compound D having molecular formula C3H6O2 shows the following spectral data.
Find out the structure.

68
 Structure Elucidation
by Integrated
Spectroscopic Methods

Fig. 14.11: Mass spectrum of compound D

Fig. 14.12: IR spectrum of compound D

Fig. 14.13: 1H ‒NMR spectrum of compound D

Solution
You can compute the IHD for the molecule to be 1 suggesting a single double bond or a
ring.

IR: The IR spectrum of this molecule shows a feature that we have not observed so far.
Let us see what information do we get from IR.
i) The intense peak close to 1700 cm‒ 1 is characteristic of the carbonyl group.
ii) The broad band around 3000 cm‒1 is characteristic of – OH stretching; probably
hydrogen bonded – OH group.

69
Miscellaneous Methods These two pieces of information indicate towards the presence of a – COOH functional
group. Let us see other spectra for more information.

NMR: We can arrive at the following observations from its NMR spectrum.
i) The NMR spectrum gives three signals indicative of three different types of
protons.
ii) The small peak at a highly downfield δ = 10.5 which is likely to be due to the
acidic proton of the − COOH.
iii) The typical pattern of a two proton quartet and three proton triplet at about δ 1.2
and δ 2.3 respectively are suggestive of – CH2CH3 group.
On the basis of the two spectra, the tentative structure of the molecule can be proposed
to be CH3CH2COOH. Let us check whether the mass spectrum supports it or not.

Mass: The mass spectrum contains the following information.

i) The molecular ion peak M+ is at m/z 74.
ii) A M −17 peak at m/z 57 is indicating the loss of – OH.
iii) The intense peak at m/z 29 could be due to the loss of COOH.
iv) The peak at m/z 45 probably arises because of COOH+ ion.
As the mass spectrum clearly accounts for the –COOH group we can say that the
proposed structure is correct. The given compound D is propanoic acid with the
following structure.
CH3CH2COOH (Propanoic acid)

Example 5
A compound E having molecular formula C5H9O2Cl exhibits the following spectra.
Suggest its structure.

Fig. 14.14: Mass spectrum of compound E

70
 Structure Elucidation
by Integrated
Spectroscopic Methods

Fig. 14.15: IR spectrum of compound E

Fig. 14.16: 1H-NMR spectrum of compound E

IHD: As usual we first calculate the IHD from the molecular formula.

9 1
IHD = 5 − − +1
2 2
= 5−5 + 1
= 1

So the molecule has a double bond or a ring. Let us see what do the spectra suggest?

IR: The following observations from IR spectrum are given below.

i) The strong band in the region 1750 – 1735 cm‒ 1 indicates C = O stretch.
ii) This along with two strong stretching absorptions in the range 1300 – 1000 cm‒1
due to C – O indicate the presence of ester function (-O-C=O)

71
Miscellaneous Methods Let us look into other spectra to identify the groups attached to the ester function.

NMR
i) The 1H-NMR spectrum shows the presence of four different types of protons.

ii) The two quartets at δ = 4.23 and at δ = 4.39 are for one proton and two protons
respectively.

iii) The other two signals, a doublet at δ = 1.68 and a triplet at δ = 1.31 are for two
protons each.

iv) One triplet and one quartet could be attributed to ethyl group (−CH2CH3).

v) The other quartet and a doublet may be due to CH3CH(Cl)‒ unit.

We are still not very sure but the tentative structure at this stage is given below.
Cl O
CH3 CH C O CH2CH3
let us see how does the mass spectrum help us.

Mass: The interpretation of the mass spectra is given below.

i) The M+ peak at m/z 136 is very-very small.

ii) The base peak at m/z = 29 suggests for the presence of – CH2CH3.

iii) The peak at m/z = 91 (M ‒ 45) is suggestive of the loss of – OCH2CH3 fragment;
the peak at m/z =45 corroborates this.

iv) The reasonably intense peak at m/z = 63 does go into support the proposed
structure as this may correspond to CH3CH(Cl)+ moiety which may be obtained
from the loss of CO from the m/z = 91 peak of CH3CH(Cl)CO+

v) The peak at m/z = 26 supports this.

Thus, we can say that the structure proposed above is correct and the given compound
has the following structure
Cl O
CH3 CH C O CH2CH3
Ethylchloropropionate

Example 6
A compound F has a molecular formula C4H11N and it exhibits the following spectra.
Determine its structure on the basis of these spectra.

72
 Fig. 14.17: Mass spectrum of compound F Structure Elucidation
by Integrated
Spectroscopic Methods

Fig. 14.18: IR spectrum of compound F

Fig. 14.19: 1H-NMR spectrum of compound F

Solution
If we calculate the IHD from the molecular formula of compound F by the formula
given below,
No. of hydrogen atoms No. of nitrogen atoms
IHD = No. of carbon atoms − + +1
2 2
We get,
11 1
IHD = 4 − + +1
2 2
10
= 5−
2
= 5−5 =0

73
Miscellaneous Methods Thus, the compound has no unsaturation or double/triple bond or rings.

Mass: The compound contains nitrogen as is evident from its molecular formula. The
molecular ion M+ peak is at m/z at 73 which is in accordance with the nitrogen rule.
The base peak at m/z 30 indicates that the compounds could be a primary amine as
primary amines gives this characteristic peak due to α -cleavage as shown below.
+ +
[R CH2 − NH 2 ] . → R • + CH 2 = N H 2
m/z = 30
IR: The interpretation of the IR signal is as follows.
i) The two bands in the range of 3500 – 3300 cm‒1 are supportive of the presence of
a primary amine as these bands could be arising due to the N – H stretching.
ii) The other amines are ruled out as the secondary amines show only one band in
this region and tertairy amines do not show any band here.
iii) The presence of amino group is supported by the broad band near 800 cm‒1 due
to the out of plane N − H bending and the C − N stretching band around 1090
cm‒1.
NMR: The 1H-NMR spectrum shows 4 sets of signals at δ= 0.92 (triplet, 3H), δ= 1.16
singlet (2H, broad), δ= 1.3 – 1.5 (multiplet, 4H) and δ= 2.7 (triplet, 2H).Let us now try
to identify the structural units present in the compound on the basis of these signals and
their splitting patterns.
i) The three proton triplet at δ 0.92 could be due to the protons of a methyl group,
next to a − CH2 group, i.e. CH3 – CH2 – .
ii) The broad singlet due to two H at δ 1.16 could be due to –NH2 protons which do
not show coupling with neighbouring protons.
iii) The two proton triplet at δ= 2.7 is quite downfield and is likely to be for a – CH2
group attached to – NH2 group. The splitting into triplet, could be due to the
presence of a neighbouring –CH2 group. This yields the following structural unit.
− CH2 − CH2 − NH2
iv) The remaining 4 protons appear as a multiplet between δ 1.3-1.5.
If we put together this unit and the CH3 − CH2 − unit, we get the structure indicated
below:
CH3CH2 CH2 CH2 NH2

Butanamine

Thus, on the basis of the spectra the compound is found to be butanamine with the
structure given above.

14.5 SUMMARY
The determination of molecular formula is an important aspect in the structure
elucidation of an organic compound. From the molecular formula, the Index of
Hydrogen Deficiency can be calculated. The knowledge of IHD helps to know about the
possibility of presence of unsaturation and/or rings in a molecule.

Different kind of information is available from various spectra of a molecule. The mass
spectral data helps us to know the molecular mass of a compound and the fragment ions

74
of the molecule. An analysis of the fragment ion peaks indicates the type of functional Structure Elucidation
groups or structural units that may be present in the molecule. The UV spectral data by Integrated
indicates about the extent of conjugation present in a compound. The IR spectral data Spectroscopic Methods
tells about different types of functional groups present in a compound. It also gives
information about the presence/absence of hydrogen bonding, substituent pattern of
aromatic rings etc. The 1H-NMR reveals the number of different types of protons
present in a molecule, their number and the electronic environment, etc.

Together, the variety of information available from different types of spectra leads us to
the elucidation of structure of an unknown compound. The structure-spectra correlation
also helps us to predict the spectral data for a given compound. The spectral studies,
thus, help a lot in structure determination and identification of compounds.

14.6 TERMINAL QUESTIONS

1. Calculate IHD for the following molecules:

(a) C6H6 (b) C4H8O2

O

(c) (d)

2. A compound G having molecular formula C6H6O exhibits the following spectra

as given in Fig. 14.20 to 14.22.

Fig. 14.20: Mass Spectrum of compound G

Fig. 14.21: IR Spectrum of compound G

75
Miscellaneous Methods

Fig.14.22: 1H-NMR Spectrum of compound G

Arrive at its structure and correlate different signals with structural units present in the
molecule.

3. Predict the important spectral signals which you would expect in the IR,
1
H-NMR and mass spectra of the following compounds:
i) Ethyl ethanoate
ii) Benzoic acid

4. Which type of spectral data will you use to differentiate between isomeric
compounds having molecular formula C3H6O?

14.7 ANSWERS

Self Assessment Questions

1. (a) 3 (b) 1 (c) 1

2. (i) UV (ii) IR (iii) Mass

Terminal Questions

1. The IHD can be calculated with the help of following formula.

 Number of hydrogen atoms 
IHD = Number of carbon atoms −  
 2 
 Number of halogen atoms   Number of nitrogen atoms 
− +  +1
 2   2 

i) IHD= (6-6/2) + 1 = 3+1 = 4

ii) IHD= (4-8/2) + 1 = 1

iii) The molecular formula for the given compound is C6H8. The corresponding
IHD is

76
 Structure Elucidation
IHD= (6-8/2) + 1= 2+1=3 by Integrated
Spectroscopic Methods
iv) The molecular formula for the given compound is C4H6O. The corresponding
IHD is

IHD= (4-6/2) + 1= 1+1=2

2. The structure of the compound G on the basis of the given spectra is

benzyl acetate

3. The most significant spectral signals expected in the IR, 1H-NMR and mass
spectra are as follows:

i) Ethylethanoate, CH3COOC2H5

Mass :

The molecular ion peak would appear at m/z = 88.

The fragment CH3CO+ is very stable and is likely to give an intense signal at m/z=43.
accordingly, we would expect a signal at M-43 i.e., at m/z =45. Other important
fragments are expected at m/z =29 and 15 (for ethyl group and methyl group).

IR :

The most important signal in the IR spectrum of ethyl eethanoate is for the carbonyl
absorption. As this is a part of the ester linkage it is expected to appear at around 1740
to 1750 cm-1.

NMR:

The NMR spectrum is expected to be quite simple. The ethyl part of the molecule
would give a combination of a triplet ( for CH3) and a quartet (for CH2). The methyl
group triplet is expected to be around δ = 1-1.5 and the CH2 quartet is likely to go
downfield to about 4 ppm.

As the other methyl group protons cannot have any coupling interactions, it is expected
to appear as a singlet around 2 ppm (due to the deshielding effect of the carbonyl
group).

ii) Benzoic acid, C6H5COOH

Mass

i) The molecular ion M+ peak is expected at m/z = 122.

ii) The loss of –OH is quite favorable and is expected to give a peak at
m/z=105

77
Miscellaneous Methods iii) Similarly, the loss of –COOH is also favourable and is expected to give a
peak at m/z=77; the expected ion being C 6 H 5+
iv) A further loss of HC = CH from C 6 H 5+ ion would yield C 4 H 3+ ion; the
peak for which may be observed at m/z 51.

IR

In benzoic acid we can expect 3-4 important signals/ features in the IR spectrum. These
are as follows:

i) Characteristic bands in the range of 1600 cm-1 for the benzene ring
ii) The carbonyl group at around 1700-1750 cm-1
ii) A broad signal about 3000 cm-1 for hydrogen bonding
iii) Characteristic pattern in the range of 700-750 cm-1 for the mono substituted
benzene.

NMR

The aromatic protons are expected as a multiplet between δ 7.4 – 7.9 due to the
difference in chemical shift positions of the ortho, meta and para protons and the
coupling between them.

The acidic proton of the –COOH group is expected to be quite downfield around 11-
12 ppm.

4. Let us first write down the structural formulae for the possible isomers of the
compound with the molecular formula, C3H6O.

O
i) CH3 C CH3

ii) H3C CH2 C O

H

iii) CH2 CH CH2 OH

iv) H3C C CH2

OH

These compounds can be differentiated by using UV-VIS, IR, NMR or Mass

spectrometry; NMR being the most convenient. The NMR of the compound
i) would give just one signal in NMR whereas the compounds ii) and iv)
would give three different signals each. On the other hand the compound iii)
would give as many as four signals. The compounds ii) and iv) can be further
differentiated by the location of the signals and the splitting pattern.

78
 Structure Elucidation
SOME USEFUL BOOKS AND WEBSITES by Integrated
Spectroscopic Methods
1. Robert M. Silverstein, Francis X. Webster and David Kiemle (2005).
Spectrometric Identification of Organic Compounds, 7th edition. Wiley.

2. William Kemp (1991). Organic Spectroscopy, 3rd edition. W.H. Freeman &
Company.

3. Douglas A. Skoog, F. James Holler and Timothy A. Nieman. (1998) Principles

of Instrumental Analysis, 5th edition. Brooks/Cole.

4. S.M. Khopkar (2008) Basic Concepts in Analytical Chemistry, 3rd edition. New
Age International publishers.

http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/nmr/nmr2.htm#nmr11

http://www.chemistry.nmsu.edu/studntres/chem435/Lab8/intro.html

http://www.chem.uic.edu/web1/ocol/spec/MS.htm

http://base-peak.wiley.com/

http://www.chem.ucla.edu/~webspectra/Solvingspectralproblems.html

79
Miscellaneous Methods
INDEX
Absorption signals 26 Sample handling 26
Acetone 26, 63 Integral modes 26
Analysers 43 Integration trace 26
Anisotropic 19, 21, 31 Isotopic peaks 39
Applications of mass spectrometry Larmor frequency 11
Qualitative applications 46 Larmor precession 10, 12
Quantitative applications 51 Longitudinal relaxation 13
Applications of NMR spectroscopy Magnetic moment 7, 8, 9
Qualitative applications 28 Magnetic sector analyzer 43
Ethanol 28 Magnitude of coupling constants 23
Methanol 30 Mass spectrum 38, 40
Benzyl alcohol 30
McLafferty rearrangement 48
Phenol 31
Mechanism of resonance 11
Base peak 39
Molecular ion 38
Benzaldehyde 67, 68
Multiplicity of spin-spin interactions 23
Boltzmann constant 9
Natural abundance 39
Boltzmann distribution law 9, 12
Nitrogen rule 46
Broad or wide line 27
Nuclear g-factor 7
Butanamine 73
Paramagnetic effect 17
Characteristics of mass spectrum 38
Pascal’s triangle 22, 23
Chemical exchange 30, 32
Permanent magnets 25
Chemical ionisation 42
Precessional motion 10, 11, 12, 34
Continuous wave spectrometry 12
Propanoic acid 69
Coupling constant 14, 23
Quantisation 8
Deshielding 15, 16, 17
Quantitative applications
Desorption sources 41 Analysis of multicomponent mixtures 27
Diamagnetic effect 16, 17 Elemental analysis 27
Direct insertion probe 41 Organic functional group analysis 28
Double focussing analysers 44 Radical cation 38
Electromagnets 25, 43 Radical ion 38
Electron ionisation 42 Relaxation mechanisms 12, 13
Ethychloropropionate 71 Representation of NMR 26
Factors affecting chemical shift Resolution or sharp line spectrum 27
Anisotropy of chemical bonds19, 20, 33 Scan 14, 15
Electronegativity 19
Shielding 15
Hydrogen bonds 21
Shielding constant 16
Field ionisation 42
Shielding mechanism 16
Field sweep method 12
Spin angular momentum quantum number 6, 7, 13, 32
Fourier transform spectroscopy 14
Spin down 9
Fourier transformation 14
Spin flip 12
Fragment ions 39
Spin up 9
Fragmentation
Spin-lattice relaxation 13, 32
by cleavage at a single bond 48
by α-cleavage in molecules with heteroatoms 48 Spin-spin coupling 21, 23
due to intramolecular rearrangement 48, 49 Spin-spin relaxation 13
Free induction decay 14, 32 Standard for chemical shift 17
Frequency sweep method 12 Structure elucidation of organic compounds 61
Gas phase sources 41 Superconducting magnets 25
Index of hydrogen deficiency 57, 58 Tetramethylsilane 17, 21, 26
Induced magnetic field 15, 16, 19 Theory of mass spectrometry 38
Instrumentation for mass spectrometry Theory of NMR spectroscopy 6
Inlet device 40, 41 Toluene 65
Ionisation chamber 40 Transducer 41
Analyser 40, 43 Transverse relaxation 13
Detector 40, 44, 45 Types of nuclei 6
Processing and output devices 40, 45 Unit of chemical shift 17
Instrumentation for NMR spectroscopy
Magnet 25
Sample probe 25
Detector system 25

80