TABLE OF CONTENT

CONTENT
Table of content
Acknowledgement
Objective
Methodology
Result and Discussion
Conclusion
Appendices
References

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1
2
3
4
5-11
12
13-16
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ACKNOWLEDGEMENT

We are really grateful because we managed to complete our case study the
Identification of Imidazole 2.42 and 2.43 using Spectroscopic Method within the time
given by the lecture Dr. Sazlinda Binti Kamaruzaman.This case study cannot be
completed without the effort and co-operation from our group member See Yan Teng,
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Tan Huey Jing, Chong Jin Mei, Charles Maigol and Slyvester Awoh. We also
sincerely thank our lecturer Dr. Emilia Binti Malek for the guidance and
encouragement in finishing this case study. Last but not least, we would to express
our gratitude to our friend who involved and help us to solve this case study.

OBJECTIVES

1. To interpret and identify two imidazole 2.42 and 2.43 using Infrared, Nuclear
Magnetic Resonance and Mass spectrometry.

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2. To differentiate between two imidazole 2.42 and 2.43 and type of chemical
present.

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METHODOLOGY

In order to solve the case study given, we have carried out some practicable
methods.
Firstly, we have paid a visit to Dr. Sazlinda and Dr. Emilia during their office
hours. Initially, all group members were not clear whether we need to show out the
exact steps to describe the ways we identified the products or we can straight away
using the method of comparison with the data provided, to figure out the product
2.42 and product 2.43. However, we able to clear our doubts about the question and
task that we should prepared, after we referred to Dr. Sazlinda and Dr.Emilia.
Secondly, we have taken some book references in order to make sure the
analysis we carried out was correct. In addition, the books provided a lot of
knowledge that we need in doing analysis. For example, the knowledge included for
our groups case study were Infrared (IR) Spectroscopy and Nuclear Magnetic
Resonance (NMR) Spectroscopy. Hence, the reference books had helped us a lot as
they made us easier to look through any relevant topics with our case study.
Thirdly, the convenience of Internet allowed us to search the related
documents or information from the worldwide sources. Although both books and
Internet can provide us the mountains of knowledge, Internet resources were easier
to receive academic updates and were easier to search the small topics that we
discussed in our group report.
Last but not least, we have carried out a few discussions among our
group members. During the discussion, we have separated the parts we were incharged, so everyone knew the parts they did, and also updated with each other
about the results we predicted.

DISCUSSION
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In order to identify structure present in imidazole 2.42 and imidazole 2.43,

spectroscopic method such as Infrared (IR) spectroscopy and Nuclear Magnetic
Resonance (NMR) are used. Infrared (IR) spectroscopy deals with the interaction
between a molecule and radiation from the IR region of the EM spectrum (IR region
= 4000 - 400 cm-1). The cm-1 unit is the wave number scale and is given by 1 /
(wavelength in cm). IR radiation causes the excitation of the vibrations of covalent
bonds within that molecule. These vibrations include the stretching and bending
modes. Next, in NMR spectroscopy. nuclei with an odd mass or odd atomic number
have "nuclear spin" (in a similar fashion to the spin of electrons). This includes 1H
and 13C. The spins of nuclei are sufficiently different that NMR experiments can be
sensitive for only one particular isotope of one particular element. The NMR
behavior of 1H and 13C nuclei has been exploited by organic chemist since they
provide valuable information that can be used to deduce the structure of organic
compounds. Proton nuclear magnetic resonance (proton NMR, hydrogen-1 NMR, or
1

H NMR) is the application of nuclear magnetic resonance in NMR spectroscopy with

respect to hydrogen-1 nuclei within the molecules of a substance, in order to

determine the structure of its molecules. In samples where natural hydrogen (H) is
used, practically all the hydrogen consists of the isotope 1H. Besides, Carbon-13
nuclear magnetic resonance most commonly known as carbon-13 NMR or 13C NMR
or sometimes simply referred to as carbon NMR is the application of nuclear
magnetic resonance (NMR) spectroscopy to carbon. It is analogous to proton NMR
(1H NMR) and allows the identification of carbon atoms in an organic molecule just
as proton NMR identifies hydrogen atoms. As such 13C NMR is an important tool in
chemical structure elucidation in organic chemistry. 13C NMR detects only the 13C
isotope of carbon, whose natural abundance is only 1.1%, because the main carbon
isotope, 12C, is not detectable by NMR since it has zero net spin. To indicate the
chemical shift of H atom and C atom for a molecule in NMR spectroscopy, there are
3 factors that cause an atom to be more deshielded, which are effects of
electronegativity of pi bond (anisotropy) and effects of hydrogen bonding. In this
case study, we are going to discuss about the effects of electronegativity and effects
of pi bond (anisotropy) that cause the chemical shift different from one another.

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Imidazole
2.42

Table 1

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Table 1 shows the results that are obtained for 2 spectroscopic method that
are used to detect the product of imidazole 2.42. For IR spectroscopy, we can detect
the presence of C-N group and C=C aromatic group from the wavenumber given. CN stretch can be found under wavenumber of 1373cm -1 and 1201cm-1. For C=C
aromatic stretch, values of 1476cm-1, 1442cm-1 and 1421cm-1 are found whereas
values of 1604cm-1 and 1523cm-1 indicate the presence of C=C aromatic bending.
For proton (1H) NMR of imidazole 2.42, we will look at the proton which is
most shielded to the proton which is most deshielded. The most shielded proton is at
H10 and H11 with chemical shift of 3.54ppm-3.60ppm (2H, m) as it has no effect of
electronegativity atom on neighbouring atom and it has only affected by a presence
of double bond on neighbouring H12 which the effect is very small. Secondly, H2 and
H3 is less shielded with values of 4.60ppm-4.67ppm (2H, m) because the effect of
electronegative nitrogen atom at the neighbouring atom. It draws the H atom causes
less electron density present around the atom; therefore, it is shifted more downfield.
Thirdly, when comparing H12 (5.88ppm-5.96ppm) and H1 (6.03ppm-6.11ppm), it can
be seen that H12 is more shielded that H1 because its neighbouring H2 and H3 are
closer to electronegativity atom N; therefore, N will withdraw electron firstly from
H12. Both H12 and H1 consist of only one hydrogen atom and they are multiplet.
Next, H4 has a value of 7.17ppm and it is singlet because according to n+1 rule, its
neighbouring atom does not have H atom so 0+1=1. It is far deshielded compared to
other H atom as its neighbouring atoms consist of electronegativity N atom which will
withdraw electron and the presence of pi bond of benzene ring (anisotropy) which
cause very large shielding (-) effects for protons placed above the ring, and smaller
deshielding (+) effects for protons to the side of it. These chemical shift effects
occur because electron circulation is stronger when the plane of the benzene ring is
perpendicular to the magnetic field than when it is parallel to it. Last but not least, the
most deshielded proton is H atoms (H5, H6, H7, H8 and H9) which is benzene ring
with values of 7.21ppm-7.80ppm because of anisotropy effects that had been
discussed earlier.
For carbon (13C) NMR of imidazole 2.42, the most shielded carbon is located
at H10 and H11 with fluorescence green colour (25.0ppm). It has the same reason
as in proton NMR whereby it only has single pi bond in its neighbouring atom that
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does not cause much effect on the carbon atom. The second most shielded C atom
is at H2 and H3 with value of 45.0ppm. Its neighbouring atom is more deshielded by
electronegative nitrogen atom and the presence of pi bond. On the other hand, C-12
and C-1 have values of 113.0ppm and 119.7ppm respectively. The small deviation in
chemical shifts are due to the factor of electronegative N atom nearer to C-1
compared to C-12. Next, for the benzene ring, carbon NMR contained have a values
of 132.0ppm, 124.8ppm, 126.7ppm and 128.5ppm. The blue colour of C atom has a
higher chemical shift of 128.5ppm because it is bonded and nearer to imidazole
group which causes it to be more deshielded compared to orange colour C-7 atom
which is far away from bonded atom. The most deshielded C atom (purple colour
dot) has a value of 142.4ppm as its neighbouring atom consists of 2 electronegative
N atom which withdraw electrons stronger compared to atom that attached to only
one N atom. Besides, it also has a double bond (pi bond) on the neighbouring atom
that causes the C atom more deshielded.

Imidazole
2.43

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Table 2

According to the IR spectrum in table 2 for imidazole 2.43, there is a moderate

peak present in the wavenumber of 1604cm-1 and 1469cm-1 and a weak peak present
in the wavenumber of 1532cm-1. These peaks are located at the range of 1600-1585
cm-1 and 1500-1400 cm-1. So, aromatic functional group is present in this imidazole
.There is a medium peak present in the wavenumber of 1427cm -1.This shown that
C-H bending is present in this molecule as the wavenumber is in the range of 14701450cm-1 . Some peaks are present in the wavelength of 1389cm -1(medium) and
1181cm-1 (weak) which are in the range of 1360cm -1 - 1080cm- , thus these indicate
the presence of C-N (stretch) functional group in this molecule. Overall, the
functional groups that present in imidazole 2.43 are aromatic, C-H bending and also
C-N (stretch).
For the NMR spectrum of 1H, proton at H1 and H12 have the chemical shift of
2.60-2.65ppm and 2 hydrogen with medium peak. Both of these are the most
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shielded hydrogen compared to others like H2 and H3 which has the same amount
of hydrogen attaches to it for it has a greater distant from nitrogen which act as an
electronegative element. As for the H2 and H3, they have chemical shift at 4.10ppm
with 2 hydrogen atoms and coupling constant J of 7.7. They are more deshielded
than H1 and H12 as they are nearer to the electronegative element, N. The chemical
shift that is 6.15ppm with 1 hydrogen (doublet and triplet) and with coupling constant
J of 10.0 is belongs to the hydrogen number 11 as the doublet and triplet present
when both side of neighboring carbon atoms are attached to hydrogen. The
hydrogen number 11 is more deshielded than those who have 2 hydrogen atoms as
it is affected by the anisotropy (effect of pi bond). For the hydrogen number 10, its
chemical shift is 6.63ppm with 1 hydrogen atom .It is more deshielded than the
proton in number 11 as it is nearer to two nitrogen atoms. The hydrogen number 4
has a chemical shift of 7.12 ppm with a hydrogen and it is a singlet. It is more
deshielded than others because it lies nearest to the electronegative element, N and
phenyl group (anisotropy effect). As for the chemical shift of 7.25-7.78ppm with 5
hydrogen atoms and medium peak, they belong to the proton of benzene group. This
is because this 5 protons are equivalent to each other and the range for proton that
is attached to aromatic ring is approximate 7-8ppm.
For the NMR spectrum of 13C, the most shielded carbon is the carbon
contains H1 and H12 with chemical shift of 23.7ppm as it has a large distance from
the electronegative element, N and it is attached to two hydrogen atoms. The carbon
contains H2 and H3 has chemical shift of 42.9 as it is less shielded than carbon that
has H1 and H12 attached to it as it is nearer to the nitrogen atom. Carbon that
contains H4 with 134.9 ppm is more deshielded as it contains only one hydrogen
atom and it is nearer to the nitrogen atom which is an electronegative element.
Chemical shift 141ppm belongs to carbon that is attached to phenyl group because it
is more shielded than carbon with no hydrogen which is nearer to two
electronegative element, nitrogen atom as nitrogen atom pulls the electron density of
proton toward itself. The chemical shift of 128.7ppm belongs to carbon with no
hydrogen attach to it in which has the range of 110-175ppm. It is more deshielded
than other carbon in the aromatic ring as it doesnt attach to any hydrogen atom.
Carbon atoms that contains H5 and H9 have chemical shift of 127.2ppm. Both
carbon atom have the same value of chemical shift as they are equivalent to each
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other. They are more deshielded than carbon that has H6 and H8 attached to it. The
chemical shift for carbon that contains H6 and H8 are 126.7ppm.The most shielded
carbon in aromatic ring is carbon that has H7 attached to it with chemical shift of
124.7ppm. The most deshielded carbon atom in this molecule is the carbon with no
hydrogen and is attached to two nitrogen atoms that pull the electron density toward
themselves with the chemical shift of 143.9ppm. The chemical shift of 119.5ppm and
114.7ppm belong to carbon with H10 and carbon with H11.They are more deshielded
than those attached to two hydrogen atoms but more shielded than those do not
have any hydrogen atom as they have one hydrogen that is attached to them.
There are some ways to differentiate imidazole 2.42 and imidazole 2.43.The
difference between imidazole 2.42 and 2.43 is due to the position of double bond as
both of them are isomers. The 1H shift for imidazole 2.42 which is H10 and H11 have
the value of 3.54-3.60ppm is more deshielded than H 1 and H12 in imidazole 2.43 with
2.60-2.65ppm.This is because the H10 and H11 in imidazole 2.42 are nearer to two
nitrogen atoms which act as electronegative elements .As for imidazole 2.43, the
value of chemical shift for H1 and H12 are 2.00-2.65ppm. H1 and H12 in imidazole
2.43 are more shielded than the H10 and H11 in imidazole 2.42 because they are near
er to one nitrogen so less electron density are pulled towards electronegative
element, that is nitrogen.

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CONCLUSION
The condensation reaction of lactam 2.36 gives two major products which is
imidazole 2.42 and imidazole 2.43. They were identified and interpreted using three
different spectrometry techniques which is infrared spectrometry (FT-IR), Nuclear
Magnetic Resonance (NMR) spectrometry and mass spectrometry. The result from
infrared spectrometry and mass spectrometry shows that they have similar molecular
mass and functional groups while the NMR spectrometry indicates the difference
between them. Their differences is the position of the double bond and the NMR
spectrum clearly shows the difference with the different types of proton and their
chemical shifts as well as the chemical shift of carbon atom in the mentioned double
bond on both structures.

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APPENDICES

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REFERENCES
1) Donald L. Pavia, Gary M. Lampman & George S. Kriz, James R. Vyvyan. ().
Introduction to Spectroscopy: 5th Edition, p. 235, 291-292. Cengage
Technology Edition.
2) R. Torregrosa, I. M. Pastor & M. Yus. (2005). Synthesis of imidazoles and
benzimidazoles. Retrieved from http://www.organicchemistry.org/synthesis/heterocycles/imidazoles.shtm
3) O. H. Oldenziel, D. Van Leusen & A. M. Van Leusen. (1977).Van Leusen
Reaction. Retrieved from http://www.organicchemistry.org/namedreactions/van-leusen-reaction.shtm
4) Alan F. Gasiecki, Thomas G. Pagano & Stevan W. Djuric. (2006). Synthesis of
fused imidazole rings by sequential van Leusen/CH bond activation.
Retrieved from
http://www.sciencedirect.com/science/article/pii/S0040403906020545
5) Nuclear Magnetic Resonance. (n.d.). Retrieved from
http://chemwiki.ucdavis.edu/Physical_Chemistry/Spectroscopy/Magnetic_Res
onance_Spectroscopies/Nuclear_Magnetic_Resonance
6) Mass Spectrometry. (n.d.). Retrieved from
http://www2.chemistry.msu.edu/faculty/reusch/virttxtjml/spectrpy/massspec/m
asspec1.htm
7) Infrared Spectroscopy. (n.d.). Retrieved from
https://www2.chemistry.msu.edu/faculty/reusch/virttxtjml/Spectrpy/InfraRed/inf
rared.htm

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