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1 IDENTIFICATION OF ORGANIC COMPOUNDS

There are more than 5 million organic compounds, the great majority of which are colourless liquids
or white solids. Identifying or at least characterising – determining some of its properties and features
– organic compounds is an important technique in the pharmaceutical industry, and in research
laboratories. Until the last forty years, chemical methods dominated this area, but they are now to a
great extent, supplanted by instrumental methods, particularly spectroscopic techniques.
This chapter concentrates on the application of spectroscopic techniques in the structure
determination of organic compounds. The instrumental aspects of these techniques are covered in
other chapters or in Applied Spectroscopy.

1.1 Chemical Tests


Solubility Tests
The principle of these tests is that a substance is most soluble in that solvent to which it is most closely
related in structure. Compounds are divided on the basis of water solubility into two main groups
(soluble and insoluble), which are then subdivided into other groups according to their solubility in
other solvents (e.g. acids and bases, ethanol and hexane). All solubility measurements are done at
room temperature with two drops of liquid or 50mg of solid in 1.5 mL of solvent.

Functional group tests


These have been extensively covered in Chemistry 3, and you should refresh your memory of the
following tests.

Test Functional Groups Giving +ve Observation For +ve Test

bromine

NaHCO3

DNP

Fehlings

Physical Parameters
This includes such things as melting point, boiling point, refractive index, density etc. These are
determined and compared to literature values. A close match to a complete set of literature values is
strong but not definite evidence for identification of a substance.
1. Identification of Organic Compounds

1.2 Spectroscopic Analysis In Structure Determination


Spectroscopic techniques have now become the main method of determining the structure of organic
substances. Sophisticated instruments are now available which greatly simplify organic structure
determination. The main techniques involved are listed below, along with the information which they
provide. Each instrument will be examined individually, but generally data from all techniques is used
and combined when determining the structure of a substance.

TABLE 1.1 Spectroscopic techniques

Spectroscopic Technique Information provided by the Technique


UV-visible spectroscopy The degree of conjugation of the molecule, and some evidence of
identity through spectral matching. Not particularly useful.
Infra-red spectroscopy The functional groups present in the molecule and a means of absolute
confirmation of identity through spectral fingerprint matching
NMR spectroscopy Details of the carbon-hydrogen framework of the molecule
Mass spectrometry The molecular mass of the substance (in many cases), the presence of
certain species (Cl, Br, and N) through isotope peaks, spectral
identification through fragmentation pattern matching.

1.3 Ultraviolet-Visible Spectroscopy


UV-visible spectrophotometry is not generally useful in qualitative analysis, as quite different
compounds can have a similar spectrum. It can still be useful however, to distinguish between
substances as only conjugated substances, and those containing unpaired electrons (those containing
N, O, and halogens) absorb in the UV-visible region above 220nm.

CLASS EXERCISE 1.1


What does the term conjugation mean?

UV-visible spectrophotometry is used in organic analysis to assess the degree of conjugation of a


molecule. What this means is that the molecule will absorb energy at longer wavelengths if it has
more conjugated double bonds. Normally at least two or more conjugated double (or triple) bonds to
produce a UV-visible absorption peak above 220 nm. For example 1,3-pentadiene exhibits an
absorption peak above 220 nm whilst the isomeric 1,4 pentadiene does not. Hence these two can be
differentiated by UV-visible spectroscopy.
Each extra conjugated double (or triple) bond adds about 15-20 nm to the wavelength of
maximum absorption. Aromatic rings – with 3 conjugated double bonds – typically absorb around
250-260 nm.
The groups with unpaired electrons, when attached to conjugated systems, significantly increase
the intensity of absorption, and slightly increase the wavelength.

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1. Identification of Organic Compounds

CLASS EXERCISE 1.2


How would the UV spectrum of phenylmethanal differ from that of phenylethanal?

O
H
H

1.4 Infrared (IR) Spectroscopy


Infra red radiation is the region of the electromagnetic spectrum between microwave and visible light.
It is the region of the electromagnetic spectrum which provides the correct amount of energy to make
the covalent bonds in some organic molecules to vibrate, bend, stretch, wag and rock.
Specific bonds absorb at specific frequencies, and by working backwards with correlation tables
(comprehensive listings of functional groups and IR frequencies) we can deduce the types of bonds
present in a molecule from its infra red spectrum. Full interpretation of an infra red spectrum is
extremely difficult, so it is normal to only look for common absorptions in key areas.

Interpreting Infra Red Spectra


The IR spectrum is simply a graph of % transmittance (which tells us how much light is absorbed)
versus frequency (usually given in wavenumbers, cm-1). Each functional group has its own
characteristic absorption (frequency and strength) which change very little from one compound to
another. This makes their identification very simple. For example the C=O group always absorbs in
the region from 1670 – 1780 cm-1, while the O-H absorption of alkanols always occurs in the region
from 3200 – 3600 cm-1, etc. All of these can be easily recognised in an infra red spectrum with a little
practice. Additionally many absorptions occur with specific shapes and intensities which also aid their
identification. The C=O group for example is generally a very strong sharp band (often the strongest in
the spectrum), whilst the O-H peak is generally broad, often with a small sharp peak at the high
wavenumber end.
Infra red spectroscopy can also be used in the identification of a molecule. The spectrum is
extremely complicated and often too difficult to interpret any meaningful information from, but it can
be used however as a “molecular fingerprint” which can be matched with literature spectra. If the
fingerprint region of a substance is identical to a literature spectrum then this can be taken as a form of
unambiguous identification, as no two substances have identical infra red spectra.
The infra red spectrum can be divided into two regions which provide the two different types of
information:
• the functional group region from 4000–1500cm-1 gives information about the functional
groups present in a molecule and can be further sub-divided,
• the fingerprint region between 1500 - 650cm-1 provides a method of identification.

Figure 1.1 shows a simple breakdown of the regions of the infrared spectrum.
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4000 2500 2000 1500 cm
Bonds to H Triple bonds Double bonds
C-H C≡C C=C
O-H C≡N C=O
N-H C=N
Functional group region Fingerprint region

FIGURE 1.1 The regions of the infra red spectrum.

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1. Identification of Organic Compounds

A correlation table (see Table 1.1) lists the important peaks for each common functional group,
allowing you to identify the presence of particular groups in a the spectrum of a compound. Figures
1.2-1.10 show the functional group region for selected examples of each type of functional group.

CLASS EXERCISE 1.3


Examine Figures 1.2-1.10 in conjunction with Table 1.2 to see what the various functional
group peaks really look like, and what some of the variations mean.

TABLE 1.2 IR correlation chart

Bond Frequency Region Relative Strength Comments


C-C-H 2800-2950 strong* strength proportional to number
of C-C-H bonds
C=C-H & Ar-H 3020-3070 weak
C≡C-H 3100-3200 medium
O-H 3400-3700 strong broad when H-bonding is
pronounced, and sharp at higher
end of range when OH free
N-H 3300-3500 medium one peak for each N-H bond in
1590-1650* medium higher region; peak marked * is
for primary amines & amides
only
C≡C 2100-2200 medium
C≡N 2200-2400 medium
C=C 1620-1660 weak-medium
Aromatic ring 1600,1580,1500,1450 medium one or more of these peaks may
not be present in spectrum
C=O 1660-1800 strong normally strongest peak in
spectrum; position dependent on
type of compound (acid halides
highest, amides lowest);
aromatic group attached lowers
frequency
COOH 3300-2600 strong very broad, due to OH group in
acid, C=O peak as normal

NO2 1500-1560 strong


1300-1350 strong

NOTE - Since C-O, C-N and C-X bonds do not yield distinctive peaks in the functional group region,
ethers, alkyl halides and tertiary amines and amides do NOT give specific characteristic IR functional
group peaks.

Figures 1.2-1.10 will be provided by your teacher in hardcopy form as the detail in the
spectra cannot be satisfactorily gained by scanning.

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1. Identification of Organic Compounds

CLASS EXERCISE 1.4


(a) Using Table 1.1, associate the spectra below with one of each of the following
substances. It may help if you draw the structures of each compound first.

1-hexene 1-hexanol 2-hexanone phenylhexane hexanoic acid 1-hexanamine

(i)

(ii)

(iii)

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1. Identification of Organic Compounds

(iv)

(v)

(vi)

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1. Identification of Organic Compounds

(b) How would you distinguish between the following pairs of compounds by their IR
spectra, assuming you couldn’t compare them to standard spectra for fingerprint
matching?
(i) methylbenzene and cyclohexane

(ii) chlorobenzene and 2-methylchlorobenzene

(iii) 1-hexanamine and N-methyl-1-hexanamine

(iv) phenylethene and phenylethyne

(v) benzoyl chloride and benzamide

(vi) 4-methylphenol and phenylmethanol

Part (c) of this exercise provided by your teacher.

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