Infrared spectroscopy
Dr. Musaab Abdallah
M.pharm quality assurance of pharmaceuticals
Infrared spectroscopy
The four primary regions of the IR spectrum:
Infrared spectroscopy
Infrared group analysis:
1. Alkanes: The spectrum show:
1. Alkanes:
a. C – H stretch occur around 3000 cm-1.
Sp3 C – H occurs at wave numbers less than 3000 cm-1 Octane
(3000 – 2840 cm -1). H
Vinylic (Sp2 – Sp), aromatic the C –H occurs at wave num- H C
H
bers greater than 3000cm-1 (3000 – 3100 cm-1).
CH2 have bending at 1465 cm-1.
CH3 have bending at 1375 cm-1.
N.B there is rocking bending associated with four or more
CH2 groups named (long chain band) occurs at 720 cm-1 .
Infrared spectroscopy
Infrared group analysis: octane
(w – s) (m)
Infrared spectroscopy
Infrared group analysis: 1-Octene
2. Alkenes: H
The spectrum shows: C
H C
= C – H: stretch for sp2 occurs at wave number greater than 3000 cm-1 H
(3095 – 3010 cm-1).
= C – H: out of plane bending occurs at (1000 – 650 cm-1).
C = C: stretch occurs at (1600 – 1660 cm-1).
N.B conjugation moves C = C stretch to lower wave number with
increased intensity.
Infrared group analysis: 1-octene
(w – m)
(w – m)
Infrared spectroscopy
Infrared group analysis:
1-Octyne
3. Alkynes: H C C
The spectrum shows
Ξ C – H: stretch occurs usually at 3300 cm-1.
C Ξ C: stretch occurs near 2150 cm-1.
N.B conjugation moves stretch to lower wave number.
Infrared spectroscopy
Infrared group analysis: 1-octyne
(m – s)
(w-m)
Infrared spectroscopy
Ethyl benzene
Infrared group analysis: H
4. Aromatics:
= C – H: stretch of sp2 C – H occurs at values greater than 3000 cm-1
(3050 – 3010 cm-1).
= C – H out of plane bending occurs at (900 – 690 cm-1) N.B these peaks
can be used to assign ring substitution pattern.
Overtone / combination bands appear between (2000 – 1667 cm-1) also
can be used to assign ring substitution pattern.
Infrared spectroscopy
Infrared group analysis: ethyl benzene
(w – m)
(w – m)
Infrared spectroscopy
G
Mono substituted
G
G
1,2 disubstituted (ortho or o-)
G
1,2 disubstituted (meta or m-)
G
G
1,4 disubstituted (para or p-)
G
Infrared spectroscopy
Infrared group analysis: 1-butanol
5. Alcohols and phenols:
H
a.
O – H:
Free bonded O – H appears as sharp peak at 3650 – 3600 cm-1
O
Appears in combination with the hydrogen bonded O – H peak when
alcohol is dissolved in a solvent.
b. The hydrogen bonded O – H is a broad peak at 3400 – 3300 cm -1.
C – O – H: bending occurs as a broad weak peak at
1440 – 1220 cm-1.
C – O: stretching occurs in the range 1260 – 1000cm-1.
N.B this band can be used to assign primary and secondary and
tertiary structure to an alcohol.
Infrared spectroscopy
Infrared group analysis: 1-butanol
(m– s)
br
Infrared spectroscopy
Infrared group analysis:
6. Ethers:
The spectrum show:
C – O: stretch between (1300 – 1000 cm-1) N.B absence Diisopropyl ether
of C = O and O – H is required to ensure that the C – O is
not due to an ester or an alcohol.
O
Phenyl alkyl ethers give two peaks at about 1250 cm-1
and 1040 cm-1, while aliphatic give one strong band at
about 1120 cm-1.
Infrared spectroscopy
Infrared group analysis: Diisopropyl ether
(s)
Break
Section
Slide
Infrared spectroscopy
Infrared group analysis:
7. Carbonyl compounds:
The carbonyl group present in:
a. Aldehydes.
b. Ketones.
c. Acids.
d. Esters.
e. Amides.
f. Acid chlorides. g. Acid anhydride.
Infrared spectroscopy
Infrared group analysis:
7. a. Aldehydes:
C=O: stretch occurs in the range from 1725-1740 cm-1 for
normal aliphatic aldehydes.
Conjugation to C=C (1700 – 1680 cm-1) for C=O and
1640 cm-1 for C=C. Cyclohexyl carboxaldehyde
Conjugation to phenyl C=O 1700 – 1660 cm-1 and the ring O
1600 – 1450 cm-1. C
H
Long conjugated system C=O 1680 cm-1.
C – H: stretch aldehyde hydrogen consist of weak bands
one at 2860 – 2800 cm-1 and the other 2760 – 2700 cm-1.
N.B it is easier to see the band at 2700 – 2760 cm-1 because
it is not obscured by the aliphatic C – H from alkyl chain.
Infrared spectroscopy
Infrared group analysis: Cyclohexyl carboxaldehyde
(w-m)
(s)
Infrared spectroscopy
Infrared group analysis:
7.b.Ketones:
The spectrum shows:
C=O: stretch appears in the range between 1720 – 1708 cm-1.
3-methyl-2-pentanone
When conjugated to C=C, 1700 – 1675 cm-1 for the C=O and
1644 – 1450 cm-1 for the C=C. O
Conjugated to phenyl group 1700 – 1680 cm-1 for the C=O, and
1600 – 1450 cm-1 for the ring.
Conjugated to with two aromatic rings 1670 – 1600 cm-1 for the C=O.
Cyclic ketones C=O, the wave number increases with decreasing ring
size. O
C
C
C : bending as (m) intensity peak range from
1300 – 1100 cm-1.
Infrared spectroscopy
Infrared group analysis: 3-methyl-2-pentanone
(s)
Infrared spectroscopy
4-phenylbutyric acid
Infrared group analysis:
7. C. Carboxylic Acids: O
The spectrum show:
C H
O
O – H: stretch usually very broad (strongly H-bonded) oc-
curs at 3400 – 2400 cm-1 and often overlaps the C–H
absorptions.
C=O: stretch very strong broad occurs at 1730 – 1700 cm-1,
conjugation moves absorption to lower wave number.
C – O: stretch occur in the range 1320 – 1210 cm-1
with medium intensity.
Infrared spectroscopy
Infrared group analysis: 4-phenylbutyric acid
(w – m)
br
(s)
(s)
Infrared spectroscopy
Infrared group analysis:
Ethyl pivalate
7. d. Esters:
O
The spectrum show:
Normal aliphatic esters C=O stretch occurs in the range O
1750 – 1735 cm-1.
Conjugated to C=C 1740 – 1715 cm-1 for the C=O
1640 – 1625 cm-1 for C=C.
Conjugated to phenyl 1740 – 1715 cm-1 for C=O
1600 – 1450 cm-1 for the ring.
Cyclic esters frequency increases with decreasing ring size.
C – O: stretch in two or more bands one stronger and broader
than others occurs in the range 1300 – 1000 cm-1.
Infrared spectroscopy
Infrared group analysis: Ethyl pivalate
(s) (s)
Infrared spectroscopy
Infrared group analysis: pivalamide
O
7. e. Amides:
NH2
C=O: stretch occurs approximately at 1680 – 1630 cm-1.
N – H:
For primary – NH2 two bands near 3350 cm-1 and 3180 cm-1.
For secondary –RNH at about 3300 cm-1.
N – H: bending occurs around 1640 – 1550 cm-1 for primary
and secondary amides.
Infrared spectroscopy
Infrared group analysis: pivalamide
(s)
(m – s)
Infrared spectroscopy
Infrared group analysis:
Acid anhydrides: Propionic
O
anhydride
O
The spectrum shows:
O
C=O: stretch always show two bands 1830 – 1800 cm-1 and
1775 – 1740 cm-1 with variable relative intensity. Conjugation
moves absorption to lower wave numbers.
Cyclic anhydrides moves absorption to ward higher wave
numbers.
C –O: stretch (multiple bands) occurs in the range
1300 – 900 cm-1.
Infrared spectroscopy
Infrared group analysis: Propionic anhydride
(s)
(s)
Infrared spectroscopy
Infrared group analysis:
2-aminopentane
H H
8. Amines: N
N – H: stretch occurs in the range 3500 – 3300 cm-1:
Primary amines: have two bands.
Secondary amines: have one band
Tertiary amines: have no N – H stretch.
N – H: bending in:
Primary amines broad band range from 1640 – 1560 cm-1.
Secondary amines: absorbs near 1500 cm-1.
C – N: stretch occurs in the range 1350 – 1000 cm-1.
Good luck
Solving problem
