Chapter 12 1

CARBON-CARBON BOND
STRETCHING
• Stronger bonds absorb at higher frequencies:
 C-C 1200 cm-1
 C=C 1660 cm-1
 CC 2200 cm-1 (weak or absent if internal)

• Conjugation lowers the frequency:

 isolated C=C 1640-1680 cm-1
 conjugated C=C 1620-1640 cm-1
 aromatic C=C approx. 1600 cm-1
 CARBON-HYDROGEN
STRETCHING
Bonds with more s character absorb at a
higher frequency.

 sp3 C-H, just below 3000 cm-1 (to the right)

 sp2 C-H, just above 3000 cm-1 (to the left)
 sp C-H, at 3300 cm-1
AN ALKANE IR
SPECTRUM
AN ALKENE IR
SPECTRUM
AN ALKYNE IR SPECTRUM

=>
 O-H AND N-H
STRETCHING
Both of these occur around 3300 cm-1, but
they look different.
Alcohol O-H, broad with rounded tip.
Secondary amine (R2NH), broad with one
sharp spike.
Primary amine (RNH2), broad with two
sharp spikes.
No signal for a tertiary amine (R3N)
AN ALCOHOL IR
SPECTRUM

=>
 AN AMINE
IR SPECTRUM

=>
 CARBONYL STRETCHING

• The C=O bond of simple ketones, aldehydes,

and carboxylic acids absorb around 1710 cm-1.
• Usually, it’s the strongest IR signal.
• Carboxylic acids will have O-H also.
• Aldehydes have two C-H signals around 2700
and 2800 cm-1.
 A KETONE
IR SPECTRUM

=>
AN ALDEHYDE
IR SPECTRUM

=>
 O-H STRETCH OF A
CARBOXYLIC ACID
This O-H absorbs broadly, 2500-3500 cm-1, due to strong hydrogen bonding.
 VARIATIONS IN
C=O ABSORPTION
• Conjugation of C=O with C=C lowers the stretching
frequency to ~1680 cm-1.

• The C=O group of an amide absorbs at an even lower

frequency, 1640-1680 cm-1.

• The C=O of an ester absorbs at a higher frequency,

~1730-1740 cm-1.

• Carbonyl groups in small rings (5 C’s or less) absorb at an

even higher frequency.
 AN AMIDE
IR SPECTRUM

=>
 CARBON - NITROGEN
STRETCHING
• C - N absorbs around 1200 cm-1.
• C = N absorbs around 1660 cm-1 and is much
stronger than the C = C absorption in the
same region.
• C  N absorbs strongly just above 2200 cm-1.
The alkyne C  C signal is much weaker and
is just below 2200 cm-1 .
 A NITRILE
IR SPECTRUM

=>
SUMMARY OF IR
ABSORPTIONS

=>
 STRENGTHS AND LIMITATIONS

• IR alone cannot determine a structure.

• Some signals may be ambiguous.
• The functional group is usually indicated.
• The absence of a signal is definite proof that
the functional group is absent.
• Correspondence with a known sample’s IR
spectrum confirms the identity of the
compound.
 Out of plane flexions in
substituted benzenes
• Mono: 770-730 y 710-690
• Di-o: 770-735
• Di-m: 810-750 y 710-690
• Di-p: 833-810
• Tri-1,2,3: 780-760 y 745-705
• Tri-1,2,4: 825-805 y 885-870
• Tri-1,3,5: 865-810 y 730-675

Chapter 12 20
 Out of plane flexions alkenes

• Mono: 995-985 y 910-905

• Di-trans: 980-965
• Di-gem: 895-885
• Di-cis: 690
• Tri: 840-790
• Tetra: None

Chapter 12 21
 Alkanes
• IR spectrum of decane (Fig 12.4)
 Alkenes
• IR spectrum of cyclohexene (Fig 12.5)
 Alkynes
• IR spectrum of 1-octyne (Fig 12.6)
 Aromatics
• IR spectrum of toluene (Fig 12.7)
Table 12.6, p.482
 Alcohols
Bond Frequency, cm-1 Intensity
O-H (free) 3600-3650 Weak
O-H (H bonded) 3200 - 3500 Medium, broad
C-O 1000 - 1250 Medium

IR spectrum of 1-hexanol (Fig 12.8)

 Ethers
• IR spectrum of dibutyl ether (Fig 12.9)
 Ethers
• IR spectrum of anisole (Fig 12.10)
 Ethers
• Ethers have an oxygen atom bonded to two carbon atoms
• Either or both of the carbon atoms may be
 sp3 hybridized: Dimethyl ether
 sp2 hybridized: Diphenyl ether, ethyl vinyl ether.
 sp hyrbridized:
 Amines
• IR spectrum of 1-butanamine (Fig
12.11)
IR of Molecules with C=O
Groups

Frequency
Carbonyl Group Vibration (cm-1 ) Intensity
O Ketones
RCR' C=O Stretching 1630-1820 Strong
O Aldehydes
RCH C=O Stretching 1630-1820 Strong
C-H Stretching 2720 Weak

O Carboxylic acids
RCOH C=O Stretching 1700-1725 Strong
O H Stretching 2500-3300 Strong (broad)
IR of Molecules with
C=O Groups
O Amides
RCNH2 C=O Stretching 1630-1680 Strong
N H Stretching 3200, 3400 Medium
(1° amides have two N-H stretches)
(2° amides have one N-H stretch)

O Carboxylic esters
RCOR' C=O Stretching 1735-1800 Strong
2
sp C O Stretching 1200-1250 Strong
s p3 C O Stretching 1000-1100 Strong
O O Acid anhydrides
RCOCR C=O Stretching 1740-1760 and Strong
1800-1850
C O Stretching 900-1300 Strong
RC N Nitriles
CN Stretching 2200-2250 Medium
Aldehydes and Ketones
• IR spectrum of menthone (Fig 12.12)
 Carbonyl groups
• The position of C=O stretching vibration is sensitive to
its molecular environment
 as ring size decreases and angle strain increases,
absorption shifts to a higher frequency
 conjugation shifts the C=O absorption to lower frequency

Chapter 12 35
 Carbonyl groups
O O O
O

-1 -1 -1 -1
1715 cm 1745 cm 1780 cm 1850 cm

O
O O
H

-1 -1 -1
1717 cm 1690 cm 1700 cm
Conjugation: shifts the C=O absorption
to lower frequency
 Carboxylic acids
• IR spectrum of pentanoic acid (Fig
12.13)
 Esters
• IR of ethyl butanoate (Fig 12.14)
 Esters:
• One of the carbons of the C-O-C group is sp2 hybridized and other sp3
hybridized.
• Esters display strong C=O stretching absorption: 1750-1800 cm-1
IR Spectra of Methylenecyclopentene ? Or 2,3-
dimethyl-2-butene?

p.490a
IR Spectra of Methylenecyclopentene ? Or 2,3-
dimethyl-2-butene?

p.490b
IR Spectra of nonane ? Or 1-hexanol?

p.490c
IR Spectra of nonane ? Or 1-hexanol?

p.491a
IR Spectra of 2-methyl-1-butanol ? Tert-butyl methyl
ether?

p.491b
IR Spectra of 2-methyl-1-butanol ? Tert-
butyl methyl ether?

p.491c
 Show how IR spectroscopy can be used
to distinguish between the compounds in each set.

.
 Show how IR spectroscopy can be used
to distinguish between the compounds in each set.