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Exercise 4 : - Infrared spectra

1. The IR spectrum of a compound of molecular formula C11H8O is given below:

a. Calculate the degree of unsaturation indicated by the molecular formula.

(2 x 11 – 8 + 2)/2 = 8

b. Using the molecular formula, list all possible functional groups.

alcohol, aldehyde, ether, ketone

c. Identify the functional group.

aldehyde

2. The IR spectrum of a compound of molecular formula C6H15N is given below:

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a. Calculate the degree of unsaturation indicated by the molecular formula.

(2 x 6 + 1 – 15 + 2)/2 = 0

b. Using the molecular formula, list all possible functional groups.

1o, 2o or 3o amine

c. Identify the functional group.

primary amine

3. The IR spectrum of a compound of molecular formula C10H12O2 is given below:

a. Calculate the degree of unsaturation indicated by the molecular formula.

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(2 x 10 – 12 + 2)/2 = 5

b. Using the molecular formula, list all possible functional groups.

alcohol, aldehyde, carboxylic acid, ester, ether, ketone,

c. Identify the two functional groups.

ketone and ether

4. The infrared spectrum of compound “A”, C3H6O, shows a peak at 1730 cm-1 and
no peak at 2726 cm-1. Suggest a structure for this compound.

5. A compound with a molecular formula C2H6O has an infrared spectrum which


shows, amongst others, a broad absorption between 3200 - 3400 cm -1 and a
peak at 1380 cm-1. Propose a structure for this compound.

CH3CH2OH

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Exemple 1 : spectre IR de la cyclohexylamine

Exemple 2 : spectre IR de la N-méthylaniline

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Spectroscopie de RMN

Voici un tableau présentant les déplacements chimiques les plus importants du proton lié à
l'azote. On a fait figurer les amides dans le tableau à titre de comparaison.

 (ppm) 0-2 2-5 5-9


Composé amines non amines aromatiques amides
aromatiques

Comme chez les alcools, le proton lié à l'azote est mobile. L'ajout de quelques gouttes d'eau
lourde entraîne le déplacement du pic correspondant.
Un moyen d'identifier les protons liés à l'azote consiste à enregistrer le spectre dans un solvant
inerte puis en présence d'acide trifluoroacétique qui protone l'amine. Le pic du proton lié à l'azote
possède un déplacement chimique plus grand dans le cation que dans l'amine.

Le spectre RMN de l'isobutylamine est donné ci-dessous à titre d'exemple. Les protons liés à
l'azote donnent un signal pour un déplacement chimique  = 1,25 ppm.

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Le spectre RMN de l'aniline présente un singulet pour  = 3,2 ppm dû aux atomes d'hydrogène
du groupe amino et un massif complexe centré sur  = 6,5 ppm correspondant aux atomes
d'hydrogène du cycle.

Spectroscopie dans l'ultraviolet et le visible


La spectroscopie dans l'ultraviolet et le visible est surtout utile pour les amines aromatiques. Le
spectre ci-dessous est celui de l'aniline.

Il est intéressant de comparer les spectres du benzène de l'aniline et de l'ion anilinium. Le tableau ci-
dessous résume les valeurs des maximums d'absorption.
Composé bande E bande B
benzène 203 nm ( = 7400) 254 nm ( = 204)
aniline 235 nm ( = 8600) 285 nm ( = 1430)
ion anilinium 203 nm ( = 7500) 254 nm ( = 169)

Le groupe NH2 déplace le maximum d'absorption des bandes B et E du cycle aromatique vers
les grandes longueurs d'onde (effet bathochrome) tandis que leur intensité est accrue (effet
hyperchrome). Ces effets peuvent être attribués à la conjugaison entre le doublet de l'azote et le
cycle. En revanche, l'ion anilinium dans lequel la résonance a disparu, possède un spectre très
comparable à celui du benzène.
Lorsque la conjugaison s'étend sur un plus grand nombre d'atomes comme dans les composés
diazoïques, la longueur d'onde du maximum d'absorption peut se trouver dans le domaine visible.

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Le composé est coloré. L'hélianthine est un composé dont la couleur dépend de l'extension du
système conjugué avec le pH.

Infrared Spectroscopy Examples

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Spectrum 1 - 1-bromodecane

1-Bromodecane has almost no functionality - just a halogen, C-C bonds, and C-H bonds.
Halogens do not appear in the 4000-1000 cm-1 window that we use for IR. Single C-C bonds
appear around 1400 cm-1, the less useful fingerprint region of an IR spectrum. The C-H bonds
involve sp3 carbons. That particular C-H bond appears just below 3000 cm-1 in the IR.
Overall, this is a very boring spectrum. Most notable is its almost complete lack of peaks,
indicating a molecule with very little functionality.

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Spectrum 2 - butyl ether

Butyl ether only contains C-C, C-H, and C-O bonds. As in the previous example, C-C single
bonds are in the fingerprint region and generally not useful for IR interpretation. C-O bonds
may or may not appear. When they do, C-O bonds show up in the 1200-1050 cm-1
neighborhood. In this example, they are not apparent to any significant degree. sp3 C-H bonds
always appear just below 3000 cm-1. As with the 1-bromodecane example, the spectrum of
butyl ether is most notable its lack of peaks. The spectrum indicates what the molecule is not
(not an alcohol, no alkene, no carbonyls, etc.) rather than what the molecule is.

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Spectrum 3 - limonene

Limonene introduces two new functional groups - an alkene and sp2 C-H bonds. Alkene C=C
stretches show up at about 1640 cm-1. The alkenes in limonene appear at 1644 cm-1. Because
of the alkene, the spectrum also shows sp2 C-H bonds. These appear just above 3000 cm-1,
specifically 3010 and 3082 cm-1 for limonene. Because limonene contains many more sp3 C-
H bonds than sp2 C-H bonds, the intensity (decrease in transmission on the y-axis) of the
signals below 3000 cm-1 is much stronger.

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Spectrum 4 - hexanoic acid

The spectrum of hexanoic acid is dominated by one peak - the O-H stretch of the carboxylic
acid in the 3000 -1 region. Acids are hard to miss because the O-H stretch is so broad. Of
course, all carboxylic acids should also show a strong C=O (carbonyl) stretch at 1710 cm-1.
The stretch for hexanoic acid appears at 1712 cm-1.

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Spectrum 5 - methyl heptanoate

Methyl heptanoate has one (maybe two) notable IR stretches. The main feature is the ester
C=O stretch. Ester C=O stretches normally appear at 1740 cm-1, and the one for methyl
heptanoate shows up at 1742 cm-1. Single bond C-O stretches are often unpredictable in their
intensity in an IR spectrum, but the C-O stretch for an ester is often fairly clear. The C-O
stretches appear in the 1200-1050 cm-1 area. Methyl heptanoate shows a C-O stretch at 1170
cm-1. Otherwise, the IR spectrum only shows the expected sp3 C-H stretches just below 3000
cm-1. As usual, the fingerprint region near 1400 cm-1 is not useful for charactization.

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Spectrum 6 - benzyl acetate

As another ester, benzyl acetate shows mostly the same IR features as methyl heptanoate.
Benzyl acetate has a C=O stretch (1741 cm-1). It also has peaks in and near the C-O region
(1027 adn 1237 cm-1). Because benzyl acetate contains an aromatic ring, its spectrum
includes sp2 C-H stretches at 3034 and 3066 cm-1. Conspicuously absent is the expected
aromatic ring signal at 1600 cm-1. Because the aromatic ring is not significantly polarized (no
polar substituents), its vibrations lead to minimal changes in the molecular dipolar.
Therefore, the aromatic vibrations show up very weakly (essentially not at all) in the IR
spectrum. Missing aromatic rings are common in IR spectroscopy if the ring only bears
simple alkyl substituents.

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Spectrum 7 - benzyl alcohol

Alcohols give strong, broad IR absorptions beyond 3000 cm-1. Although not as intense as
acid o-H stretches, an alcohols are nontheless very clear in a spectrum. Beyond the O-H
stretch, the spectrum of benzyl alcohol has little to offer. The molecule contains both sp2 C-H
and sp3 C-H bonds at >3000 and <3000 cm-1, respectively. As with benzyl acetate, the
aromatic ring does not appear in the spectrum of benzyl alcohol. The ring, with only carbon
substituents, has minimal polarization, so its stretch is of very weak intensity in the spectrum.

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Spectrum 8 - 4-pentyn-1-ol

Alkynes are weak in an IR spectrum, but they still stand out in a normally empty region. 4-
Pentyn-1-ol has its alkyne (C≡C) stretch at 2117 cm-1. Alkynes normally show up just below
2200 cm-1, but they are normally only visible if the alkyne is terminal (has a C-H). Internal
alkynes are typically weakly polarized and do not appear. 4-Pentyn-1-ol also has a nice
alcohol stretch beyond 3000 cm-1. The sp C-H of the alkyne caps off the alcohol peak at 3294
cm-1. If a C≡C stretch is visible below 2200 cm-1, the the sp C-H should be present also. A
final note on this spectrum is the pair of CO2 peaks around 2300 cm-1. CO2 is a common
impurity in IR spectra, and one should learn to recognize and ignore its peaks.

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Spectrum 9 - acetophenone

Acetophenone, as a ketone, should have a C=O stretch at about 1710 cm-1. Oddly, the peak
instead appears at 1689 cm-1, a full 20 cm-1 out of position. In the case of acetophenone, the
carbonyl is conjugated with the double bonds of the aromatic ring. The stretches of
conjugated pi-bonds shift in an IR spectrum by approximately 20 cm-1. Unlike the previous
molecules with aromatic rings on this page, the benzene ring of acetophenone does appear
right where it should, at 1600 cm-1. Because the ring is substituted with a polarized group (the
C=O), the ring itself is more polarized, and it's stretches appear more strongly in the IR
spectrum.

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Spectrum 10 - benzaldehyde

As an aldehyde, benzaldehyde should have two characteristic sets of peaks - a C=O stretch at
1710 cm-1 and a pair of special C-H stretches in the 2700 and 2800 cm-1 region. This IR
spectrum has the C-H stretches, but the carbonyl is shifted to 1697 cm-1. This is an example
of a conjugated carbonyl being moved from 1710 cm-1 down to a lower number. The
aromatic ring of benzaldehyde is polarized by the carbonyl group and appears at 1599 cm-1.
The broad lump in the >3000 cm-1 area is not from benzaldehyde. Aldehydes are notorious
for oxidizing to carboxylic acids during long-term storage. This sample of benzaldehyde
likely contains benzoic acid, which should have a very strong and broad absorption above
3000 cm-1. The lesson here is to always beware of impurities.

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Spectrum 11 - ethyl cyanoacetate

The strongest absorbance in the IR spectrum of ethyl cyanoacetate is its ester at 1744 cm-1.
The nitrile (cyano group or C≡N) is also clear at 2265 cm-1. Nitriles appear just above 2200
cm-1. Other, perhaps less notable, peaks include both 1028 and 1200 cm-1, each might be a
candidate for C-O stretches from the ester. The broad peak at 3454 cm-1 is not consistent with
the structure of ethyl cyanoacetate. This peak has a couple possible explanations with the
simplest being water impurities in the sample. Water in a sample will always give an
unexpected O-H stretch.

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Spectrum 12 - 2,6-dimethylaniline

Introductory treatments of IR spectroscopy rarely include compounds that contain nitrogen.


Amines are actually common functional groups. The C-N bond of amines appear in the
fingerprint region and is not useful for functional group identification. The N-H bonds,
however, show clearly in the >3000 cm-1 area. N-H stretches are broad like O-Hs, but they
are not quite as strong. Primary amines have an NH2 group and show two separate N-H
stretches. Secondary amines only have a single N-H and give just one N-H stretch. Tertiary
amines have no N-Hs and therefore do not show any broad signals beyond 3000 cm-1. The
NH2 of 2,6-dimethylaniline gives two clear N-H stretches at 3467 and 3390 cm-1. The
molecules also has C-H stretches above and below 3000 cm-1 because of the sp3 and sp2 C-H
bonds. The aromatic ring appears at 1622 cm-1, which is higher than one would normally see
an aromatic ring C=C stretch. Finally, this sample shows a fairly large CO2 impurity around
2300 cm-1.

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