Subject Chemistry

Paper No and Title 12: Organic Spectroscopy

Module No and 35: Combined problem on UV, IR, 1H NMR, 13C

Title NMR and Mass – Part VII
Module Tag CHE_P12_M35

CHEMISTRY PAPER No. 12: Organic Spectroscopy

MODULE No. 35: Combined problem on UV, IR, 1H NMR, 13C NMR
and Mass- Part VII
 TABLE OF CONTENTS
1. Learning Outcomes
2. Introduction
3. Problems and their solutions

CHEMISTRY PAPER No. 12: Organic Spectroscopy

MODULE No. 35: Combined problem on UV, IR, 1H NMR, 13C NMR
and Mass- Part VII
 1. Learning Outcomes

After studying this module, you shall be able to

 Solve problem related with electronic transitions

 Learn how to differentiate molecule on the basis of IR spectroscopy
 Correlate spectra with structure of compound
 Interpret the spectroscopic data

2. Introduction

The knowledge and concepts of UV-visible, IR, 1H NMR, 13

C NMR and Mass help us in
solving problems based on the experimental data. It will help us in analysing the
experimental data to elucidate the structure of any organic compound.

While analysing the data the following point must be kept in mind:

 In UV-visible spectroscopy; the types of bonds and electrons plays important role in
understanding the electronic transitions.
 UV-visible spectroscopy gives information regarding the presence of conjugation,
carbonyl group etc.
 The IR values gives information regarding the functional group present in the
molecule
 The 1H NMR tells us the number and environment of neighbouring hydrogens
present.
 The 13
C NMR helps in getting the information about the type of carbon atom(s)
present in the molecule.
 Mass spectral data gives information about the total mass and fragmentation pattern of
the molecule.

CHEMISTRY PAPER No. 12: Organic Spectroscopy

MODULE No. 35: Combined problem on UV, IR, 1H NMR, 13C NMR
and Mass- Part VII
 By combining all the information one can find the structure of the molecule.

3. Problems and their solutions

Q. 1. Which of the following has the highest carbonyl stretching frequency.

A. 1. Except acetamide, the inductive effect is dominant and the highest carbonyl
stretching frequency will be shown by (b) because it involves the largest net inductive
withdrawal from the carbonyl group.

Q. 2. The proton-decoupled spectrum of a tribromobenzene (C6H3Br3) consists of two signals

only. What tribromobenzenes is it?
A. 2. There are three possible tribromobenzenes:

CHEMISTRY PAPER No. 12: Organic Spectroscopy

MODULE No. 35: Combined problem on UV, IR, 1H NMR, 13C NMR
and Mass- Part VII
 The presence of two signals indicates that only two different types of carbon atoms are
present in the compound. Only 1,3,5-tribromobenzene has a degree of symmetry such that it
would give only two signals and, therefore, it is the correct structure.

Q. 3. Predict the structure of the compound whose peaks in the mass spectrum have m/e
values 57 (100% abundance), 41, 29 and 27.
A. 3. The predicted structure of the compound is:

Q. 4. A compound with molecular weight 116 gave the following general information:
(i) UV: 283 mµ Ɛmax 22.
(ii) IR: 3000-2500 (b) 1715 (s), 1342 cm-1 (w)
(iii) NMR: 7.88 τ singlet (3H), 7.40 τ triplet (2H), 7.75 τ triplet (2H) and -1.1 τ singlet (1H).
Find the structural formula of the compound. (Note: δ=10-τ)

A. 4. In the UV spectrum, the absorption at 283 mµ of low intensity indicates the

presence of carbonyl group.
The presence of carbonyl group is further confirmed by a strong band at 1715 cm-1. A very
broad band at 3000-2500 cm-1 is most characteristic of acids (O-H stretching and it appears as
a result of strong hydrogen bonding.
The presence of an acid group (-COOH) is also shown by NMR which gives a signal (singlet)
at the negative tau value. Thus, the compound under investigation contains:
(i) –CO- group and
(ii) –COOH group
Further, two triplets result at 7.40 τ and 7.75 τ having the same integral area. It must be due to
–CH2-CH2-, clearly, two methylene groups must be under the different environments and
thus, couple to give rise to two triplets. The appearance of a three proton singlet at 7.88 τ

CHEMISTRY PAPER No. 12: Organic Spectroscopy

MODULE No. 35: Combined problem on UV, IR, 1H NMR, 13C NMR
and Mass- Part VII
 must be a methyl group attached with the carbonyl group. Hence, the compound under
investigation is

Q. 5. An organic compound forms a molecular ion peak in its mass spectrum at m/e 114. The
other prominent peaks appear at m/e 85, 72 (M. R. ion), 57, 41, 29. Name the compound.

A. 5. The possible structure of the compound would be:

Q. 6. The compound has the molecular formula C5H7NO2. Following are the infrared, 1H
NMR and 13C NMR spectra.

CHEMISTRY PAPER No. 12: Organic Spectroscopy

MODULE No. 35: Combined problem on UV, IR, 1H NMR, 13C NMR
and Mass- Part VII
 A. 6. We calculate the index of hydrogen deficiency of three. A quick glance at the
infrared spectrum reveals the source of unsaturation implied by an index of three: a
nitrile group at 2260 cm-1 (unsaturation index = two) and a carbonyl group at 1747
cm-1 (unsaturation index = one). The frequency of the carbonyl absorption indicates an
unconjugated ester. The appearance of several strong C-O bands near 1200 cm-1
confirms the presence of an ester functional group. We can rule out bond
because they usually absorb at a value of 2150 cm-1 and have a weaker intensity than
compounds that contain bond.
13
The C NMR spectrum shows five peaks and thus is consistent with the molecular
formula which contains five carbon atoms. Notice that the carbon atom in the
group has a characteristic value at 113 ppm. In addition, the carbon atom in the ester C=O
appears at 163 ppm. One of the remaining carbon atoms (63 ppm) probably lies next to an

CHEMISTRY PAPER No. 12: Organic Spectroscopy

MODULE No. 35: Combined problem on UV, IR, 1H NMR, 13C NMR
and Mass- Part VII
 electronegative oxygen atom. The remaining two carbon atoms, which absorb at 25 and
14 ppm, are attributed to the remaining methylene and methyl carbons. The structure is:

The 1H NMR spectrum shows a classic ethyl pattern: a quartet (2H) at 4.3 ppm and a
triplet (3H) at 1.3 ppm. The quartet is strongly influenced by the electronegative oxygen
atom, which shifts it downfield. There is a two proton singlet at 3.5 ppm.

Q. 7. Calculate the chemical shift in parts per million (δ) for a proton that has a resonance
of 128 Hz downfield from TMS on a spectrometer that operates at 60 MHz.
A. 7. This can be calculated from the following formula:
ppm = Value of resonance frequency in Hz
Value of frequency that instrument operates on

Thus substituting the values in the above equation we get the value of ppm as 2.1 ppm.

CHEMISTRY PAPER No. 12: Organic Spectroscopy

MODULE No. 35: Combined problem on UV, IR, 1H NMR, 13C NMR
and Mass- Part VII