Organic Chemistry Laboratory 1

IR & NMR Practice Problems

1) Draw that functional group! (Assume it is attached to a methyl group, e.g.: H3C—R,
where R is your functional group.)

a) a tert-butyl ether f) a phenylamine

b) a diethylamide g) a phenol
c) an aldehyde h) a methylcarbamate
d) a methyl ester i) an allyl group
e) a hydroxyl j) a vinyl group

Chemical Equivalency:
Two or more protons that are in the same chemical environment are said to be
“chemically equivalent.” You can tell if they are in the same chemical environment if, (a)
they are all attached to the same atom and that atom can rotate freely, and/or (b) they
mirror protons on another atom. For example, look at isopropanol:

OH Inequivalent
H
H3C CH3

Equivalent

The protons on the two methyl groups are equivalent, the proton on the central carbon is
inequivalent from either of those on the methyls. As another example, look at styrene:

Equivalent
Equivalent Inequivalent
H Hc
H Ha

Hb
H H Inequivalent
H

The protons that mirror each other on the phenyl group are chemically equivalent,
because the phenyl group can rotate freely around the single bond attaching it to the vinyl
group. On the other hand, Ha and Hb, which are attached to the end of the vinyl group are
inequivalent, because the double bond cannot rotate freely. Therefore, Ha will always be
cis to Hc, and Hb will always be trans to Hc.
2) Armed with this information and based on the final example below, label the protons
on the ten molecules in the table. State the number of different protons and indicate
which protons are chemically equivalent by labeling them with different letters.
Because these are line angle drawings, you will need to draw in the protons attached
to carbon. (Don’t forget the octet rule!) Pay attention to stereochemistry and possible
resonance structures. (See McMurray, Ch. 9 for details on stereochemistry.)
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IR & NMR Practice Problems
Cl Cl
= Cl

Cl

Below, there are four different sets of protons, labeled Ha, Hb, Hc, and Hd.

Cl Cl
Hc Hc
CHb3 = Cl
Ha3C Ha3C
Hd Hd
Cl CHb3

We must rotate around the central bond to check for symmetry. The dotted line shows
a possible mirror plane. On either side of it, however, the molecule is asymmetric.
Therefore, all protons attached to different atoms will be in different chemical
environments. You might find it helpful to make a model of this molecule and/or
some of the other molecules in the table below in order to help you visualize them.

H2N Br

Br
Na

O
O
O OH
OH
O
NH

O
OH
H3C Br
HO
O
O
Me H
F Et
MeO OMe

Infrared Spectroscopy (IR):

IR is spectroscopic method that is generally used for identifying the functional groups in
a molecule. When a molecule absorbs infrared light, the electrons in its bonds are excited
into higher vibrational energy levels. Different types of bonds (and therefore different
functional groups) absorb light at different wavelengths in the infrared region of the
electromagnetic spectrum.
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IR & NMR Practice Problems
Below is a typical IR Spectra (Food Chemistry, 109 (2), 2008, 293–298). It is of the
molecule salicylaldehyde:
H O

OH

The ‘Y’ axis of the graph represents the “% transmittance, %T”—the amount of light that
is able to pass through the sample. A transmittance of 100% occurs when the light is able
to pass through the sample without interacting with the molecule. Peaks in the IR Spectra
appear at places where the transmittance is <100%. The ‘X’ axis of the graph represents
the “wavenumber, cm-1”—a measure of frequency and the inverse of the wavelength of
light in units 1/cm. Larger wavenumbers represent higher energy vibrational transitions.
The amount of energy it takes depends, again, on the type of bond. For example, the C-H
bond of the aldehyde functionality in salicylaldehyde appears at 2848 cm-1, whereas the
C=O bond appears at 1662 cm-1. Many different types of bonds appear in the IR between
1500 cm-1 and 500 cm-1. It is often difficult to assign these peaks to specific bond types
because of the complexity of this region, which is known as the “fingerprint region.”
3) You will find a list of common IR stretching frequencies in the IR/NMR folder on
CourseWorks. Use this list to match the molecules below to their IR spectra. Pay
attention to peak intensity and to functional groups whose stretching or bending
frequencies appear outside of the fingerprint region (carbonyls including aldehydes,
ketones, esters, amides, and carboxylic acids; nitriles; alkynes; alcohols).
Organic Chemistry Laboratory 4
IR & NMR Practice Problems
(i)
O

O
HO OH
OH O
O O

(A)

(B)

(C)
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IR & NMR Practice Problems
(ii)
N

O NH2
NH
HO O
OH O N
O NH2 OH O O

(A)

(B)

(C)

(D)
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IR & NMR Practice Problems

(iii)

N
Br
O
NH H O Cl OH OH
MeO OMe NH OH
HN OH Br HO
H S O O NH2 OH OH

(A)

(B)

(C)
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IR & NMR Practice Problems
(D)

Nuclear Magnetic Resonance Spectroscopy (NMR):

NMR is a powerful spectroscopic tool used to determine the identity of molecules. In this
course, we will focus on proton (1H) NMR. Depending on their chemical environments
(the types of functional groups nearby, the hybridization of their carbon), different
protons have different chemical shifts in the NMR spectra. Another way of saying this is:
all “chemically equivalent” protons will have the same chemical shift, and all
“chemically inequivalent” protons will have different chemical shifts. You will find
tables of chemical shifts for different types of protons in the “Spectroscopy” folder on
CourseWorks.

The chemical shift is given in parts-per-million, or PPM. Higher chemical shifts occur in
the “downfield” region of the NMR spectra. Protons in this region are said to be
“deshielded” from the magnetic field produced by the spectrometer. Lower chemical
shifts occur in the “upfield” region. Protons in this region are said to be “shielded” from
the magnetic field. In general, electron withdrawing groups and more electronegative
atoms will deshield a proton, whereas electron donating groups will shield it.

The area under the peaks in an NMR spectra—known as the integration value—tells you
the relative number of protons with a particular chemical shift and, therefore, the
empirical formula for the protons in the molecule. The “splitting” of the peak will tell you
the number of protons on neighboring carbons. Generally, this is equal to N + 1. (More
complex splitting patterns are observed for aryl rings and olefins.) We say that these
neighboring protons are “coupled” to our proton(s) of interest. As an example, let’s look
at the 1H NMR for ethyl acetate:1
O HA HA
HB HC
O
HB HC
HB HC

                                                                                                               
1
All the NMRs here are predicted by ChemBioDraw, and may not match experimentally produced spectra exactly.
Organic Chemistry Laboratory 8
IR & NMR Practice Problems

DOWNFIELD UPFIELD

First look at peak A. It has a relatively downfield chemical shift of ~4.2 PPM, indicating
that the carbon containing these protons is bound to an electronegative atom. It has an
integration value of 2, indicating that it represents two protons (or a multiple of 2
protons). It is split four times (into a quartet), indicating that it is coupled to three other
protons. We therefore can assign this peak as the methylene (CH2 group) on ethyl acetate.
Peak B is a singlet—a single peak with no splitting. Peak C is a triplet. Using a similar
analysis to the one we used for peak A above, we can assign them as is shown above.

4) For the molecules pictured, identify each proton on the in the NMR spectra below.
Label each peak as a singlet, doublet, triplet, etc. The numbers represent the relative
integration of each peak.

Cl

a) Cl
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IR & NMR Practice Problems
b)
O
CH3
O NH

c)
O

O OH

O
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IR & NMR Practice Problems
d)
O

N N

O N N

5) Determine each molecule’s structure given its 1H NMR spectra and molecular
formula.

a) C4H10O
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IR & NMR Practice Problems
b) C4H6O

c) C5H8Br4

d) C8H8O2
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IR & NMR Practice Problems
e) C4H8O

f) C8H8Cl2O