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Infrared Spectroscopy
Carbonyl Compounds
O O O O O O O O O O
R O R R Cl R O R R OR R H R R R OH R NR2
1810 cm-1 1800 cm-1 1760 cm-1 1735 cm-1 1725 cm-1 1715 cm-1 1710 cm-1 1690 cm-1
(band 1) (band 2)
both present
Inductive Effects Resonance Effects
stronger O
bond O O
R W R W
R W
stronger
bond
weaker weaker
O bond O O bond
R D R D R D
Carbonyl Compounds
O O O O O O O O O O
R O R R Cl R O R R OR R H R R R OH R NR2
1810 cm-1 1800 cm-1 1760 cm-1 1735 cm-1 1725 cm-1 1715 cm-1 1710 cm-1 1690 cm-1
(band 1) (band 2)
both present
Inductive Effects Hydrogen Bonding
H O H O
H C R R
O
H O H O
H weaker weaker
bond bond
O O
Carbonyl Compounds
Other Factors that Influence Position of C=O Absorbance
1. Conjugation
• conjugation shifts carbonyl absorbance right 25-45 cm-1; additional unsaturation 15 cm-1
O O O
O O O
H H OH
OH
1727 cm-1 1703 cm-1 1716 cm-1 1690 cm-1 1712 cm-1 1687 cm-1
may see two bands
O R
R O
s-cis s-trans
Carbonyl Compounds
1-penten-2-one
C=C
C=O
Carbonyl Compounds
2. Ring Size (Angle Strain)

• decreasing ring size shifts carbonyl absorbance to higher frequencies
O O O O
O O
1717 cm-1 1747 cm-1 1735 cm-1 1770 cm-1
O O
NH NH
1666 cm-1 1700 cm-1

Carbonyl Compounds
3. Alpha Substituion
• the presence of an electronegative group at the a position shifts the C=O
stretch to the right (10-45 cm-1)
O O
Cl
1715 cm-1 1726 cm-1
• influence by both inductive and field effects
O O
δ-
X X
δ+ δ-
δ+
X withdraws electron density from carbonyl repulsion of nonbonding electrons on O

(inductive effect) (field effect)
strengthens C=O bond strengthens C=O bond
Carbonyl Compounds
3. Alpha Substituion
• magnitude of shift is influenced by conformation
O Cl OH O R'
H R' R' Cl Cl H
R R R
A B C
syn-eclipsed (cis) anti-staggered (gauche)
O O O
H Cl H
H H Cl
1713 cm-1 1750 cm-1 1725 cm-1
• may see multiple absorbances

Carbonyl Compounds
methyl chloroacetate
O
Cl
OCH3
C=O
Carbonyl Compounds
4. Internal Hydrogen-Bonding
• effects can be additive
O O
OMe OMe
OMe OH
1729 cm-1 1680 cm-1

Aldehydes
• C=O stretch between 1740-1720 cm-1

- typically about 1725 cm-1 for aliphatic aldehydes
- absorbance is lowered by conjugation
• conjugated aldehydes: 1700-1660 cm-1
• C-H stretch of CHO shows two weak bands (2860-2800 and 2760-2700 cm-1)
- first band may be obscured by sp3 C-H absorbances
Aldehydes
octanal
Aldehydes
crotonaldehyde
Ketones

- typically about 1715 cm-1 for aliphatic ketones
- absorbance is lowered by conjugation
• conjugated ketones: 1700-1680 cm-1; or lower if doubly conjugated
- frequency increases with decreasing ring size
• bending vibration appears as medium intensity peak between 1300-1100 cm-1
• 1,3-diketones give more complicated spectra

Ketones
cyclohexanone
overtone
C=O
Ketones
mesityl oxide
H
O O O O
Ketones keto form enol form
1723 and 1706 cm-1 1622 and 3200-2400 cm-1
2,4-pentanedione
O-H
O O OH O
C=O
(ketone) C=O
(enol)
Carboxylic Acids
• O-H stretch between 3400-2400 cm-1

- typically very broad
- absorbance often centered about sp3 C-H region
• C=O stretch appears between 1730-1700 cm-1

- strong, usually more intense than than of aldehydes and ketones
- conjugation moves absorption to lower frequency
• C-O stretch between 1320-1210 cm-1

Carboxylic Acids
isobutyric acid
Carboxylic Acids
benzoic acid (nujol)

Carboxylic Acids
benzoic acid
OH
1-octanol
OH
O O
Carboxylic Acids R O R O
sodium benzoate
O- +Na
symmetric asymmetric
stretch stretch
Esters
• C=O stretch appears between 1750-1735 cm-1

- conjugation with C=O moves absorption to lower frequencies (10-25 cm-1)
O
OR (band moves to right)
- conjugation with ester oxygen moves band to higher frequencies (15-25 cm-1)
O (band moves to left)
R O
- frequency increases with decreasing ring size
• C-O stretch gives two bands between 1300-1100 cm-1

- one often stronger than the other
Esters
ethyl acetate
OCH2CH3
C=O
C-O
1743 cm-1
Esters
methyl benzoate
1724 cm-1
O O
Esters R O R O
phenylacetate
C=O C-O
1765 cm-1
Esters
Effect of Ring Size & Conjugation on C=O Absorbance
effect of effect of
ring size effects α,β-conjugation conjugation with O
O O O
O O O
1735 cm-1 1725 cm-1 1760 cm-1
O O O
O O O
1770 cm-1 1750 cm-1 1800 cm-1
O
1820 cm-1
Amides
• N-H stretch occurs between 3500-3300 cm-1

- signal varies with amide structure
• 1 amines show two bands (~3350 and 3180 cm-1)
• 2 amines have one band (~3300 cm-1)
• 3 amines have no absorbance in this region
• N-H bend vibrations between 1640-1550 cm-1
O O O
H H R
R N R N R N
H R R
1° 2° 3°
Amides
isobutylamide
NH2
NH2 C=O
Amides
N-methylacetamide
Amides
N,N-dimethylacetamide
O
CH3
N
CH3
Amides
Effect of Ring Size on C=O Absorbance
O
O
O
NH
NH
NH
1660 cm-1 1705 cm-1 1745 cm-1

Acid Chlorides
• C=O stretch occurs between 1810-1775 cm-1

- conjugation shifts frequency to right (1780-1760 cm-1)
• C-Cl stretch between 730-550 cm-1

Acid Chlorides
acetyl chloride
benzoyl chloride
Acid Anhydrides
• C=O stretch always has two bands

- absorption at 1830-1800 and 1775-1740 cm-1
• may vary in size
- conjugation shifts frequency to right (lower frequency)
- ring strain moves absorption to left (higher frequency)
• C-O stretch - multiple bands between 1300-900 cm-1

Anhydrides
propionic anhydride
Imines, Oximes, and Hydrazones
R' OH NR'2
N N N
R R R R R R
imine oxime hydrazone
C=N 1690-1640 cm-1 1650-1610 cm-1

OH 3650-2600 cm-1
http://www.ochemonline.com/Infrared_spectroscopy_absorption_table
Imines, Oximes, Hydrazones
2-butanone oxime
OH
N
C=N
N-OH (1665 cm-1)
Imines, Oximes, Hydrazones
acetone dimethylhydrazone
NMe2
N
C=N
benzaldehyde phenylhydrazone
H
N
N Ph
N-H
C=N
(1602, 1593 cm-1)
Nitriles, Isocyanates, and Related Compounds
+ -
R C N R N C O R N N N R N C N R R N C S
nitrile isocyanate azide carbodiimide isothiocyanate
2250 cm-1 2270 cm-1 2140 cm-1 2130 cm-1 2125 cm-1
(broad)
R R'
C C C O C O
R R'
allene carbon dioxide
1950 cm-1 2349 cm-1

(medium)
Nitriles
cyclohexanecarbonitrile
C≡N
o-tolunitrile
C≡N
Isocyanate and Isothiocyanate
butyl isocyanate
N=C=O
cyclohexane isothiocyanate
N=C=S
Azides and Carbodiimides
ethyl 2-azidoisovalerate
N3
N,N’-dicyclohexylcarbodiimide
N=C=N
Allenes
1,2-pentadiene
H H
C C C
CH3CH2 H
sp2 C-H
C=N
N-OH C=C=C
Other Groups
R F R Cl R Br R I
fluorides chloride bromide iodide
1400-1000 cm-1 785-540 cm-1 650-510 cm-1 600-485 cm-1
R NO2 Ar NO2 R SH
nitro group nitro group thiol
1600-1530 cm-1 1550-1490 cm-1 2550 cm-1

1390-1300 cm-1 1355-1315 cm-1
Halides
carbontetrachloride
iodoform
I
H C I
I
C-I
stretch
Halides
chloroform
chloroform-d
C-D Cl
D C Cl
Cl
Nitro Compounds
2-nitropropane
O O
N
NO2
Thiols
butanethiol
S-H
What Can the IR Tell You?
Evaluation of Unknown Samples by IR
• Preliminary Evaluation: Identification of Major Functional Groups
- Determine what you might expect to see (peak position, # of peaks) for each of the possible
major organic functional groups.
- Determine which functional groups are potentially present. Is there a peak between 3600-3000 cm-1?
Consider and alcohol or amine – how can you differentiate the two?
- You may also be able to eliminate possibilities based on peaks that are not present (e.g. no C=O
stretch? esters, carboxylic acids, aldehydes and ketones are eliminated from consideration).
- Consider also any special circumstances that could affect what you see (e.g. hydrogen bonding,
amine substitution, etc.)
• Subsequent Evaluation: Indications of Minor Functional Groups
- Consider the presence of minor functional groups including double and triple bonds, halides,
nitro groups, ethers, etc.
- Be very careful here. IR spectra are usually very complex. Don't try to read more into the spectrum
than is actually there.
Practice Problem 1
What does this IR tell you about structure?
C8H12O
Practice Problem 1
what does this IR tell you about structure?
C8H12O (same compound, now IR taken as solution in CCl4)

3429 70 2817 29 1602 30 1248 74 913 52
3085 53 2766 64 1584 60 1184 72 892 49
3065 42 2719 37 1493 12 1156 74 865 35
Infrared Spectroscopy 3030 31 1953 77 1453 13 1120 60 760 12
2979 20 1807 72 1391 38 1067 41 701 5
2956 33 1734 6 1373 55 1022 17 616 77
Practice Problem 2 2876 41 1724 4 1301 66 1000 58 526 30
What does this IR tell you about structure?
C9H10O

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Infrared Spectroscopy

Inductive Effects Resonance Effects

Inductive Effects Hydrogen Bonding

Other Factors that Influence Position of C=O Absorbance

may see two bands

Other Factors that Influence Position of C=O Absorbance

2. Ring Size (Angle Strain)

1717 cm-1 1747 cm-1 1735 cm-1 1770 cm-1

1666 cm-1 1700 cm-1

Other Factors that Influence Position of C=O Absorbance

1715 cm-1 1726 cm-1

• influence by both inductive and field effects

X withdraws electron density from carbonyl repulsion of nonbonding electrons on O

Other Factors that Influence Position of C=O Absorbance

• may see multiple absorbances

Other Factors that Influence Position of C=O Absorbance

1729 cm-1 1680 cm-1

• C=O stretch between 1740-1720 cm-1

• C=O stretch between 1720-1708 cm-1

• bending vibration appears as medium intensity peak between 1300-1100 cm-1

• 1,3-diketones give more complicated spectra

• O-H stretch between 3400-2400 cm-1

• C=O stretch appears between 1730-1700 cm-1

• C-O stretch between 1320-1210 cm-1

benzoic acid (nujol)

• C=O stretch appears between 1750-1735 cm-1

OR (band moves to right)

O (band moves to left)

- frequency increases with decreasing ring size

• C-O stretch gives two bands between 1300-1100 cm-1

Effect of Ring Size & Conjugation on C=O Absorbance

1735 cm-1 1725 cm-1 1760 cm-1

1770 cm-1 1750 cm-1 1800 cm-1

• C=O stretch between 1680-1630 cm-1

• N-H stretch occurs between 3500-3300 cm-1

• N-H bend vibrations between 1640-1550 cm-1

Effect of Ring Size on C=O Absorbance

1660 cm-1 1705 cm-1 1745 cm-1

• C=O stretch occurs between 1810-1775 cm-1

• C-Cl stretch between 730-550 cm-1

• C=O stretch always has two bands

• C-O stretch - multiple bands between 1300-900 cm-1

C=N 1690-1640 cm-1 1650-1610 cm-1

nitrile isocyanate azide carbodiimide isothiocyanate

1950 cm-1 2349 cm-1

fluorides chloride bromide iodide

1400-1000 cm-1 785-540 cm-1 650-510 cm-1 600-485 cm-1

nitro group nitro group thiol

1600-1530 cm-1 1550-1490 cm-1 2550 cm-1

Evaluation of Unknown Samples by IR

• Preliminary Evaluation: Identification of Major Functional Groups

• Subsequent Evaluation: Indications of Minor Functional Groups

What does this IR tell you about structure?

what does this IR tell you about structure?

C8H12O (same compound, now IR taken as solution in CCl4)

What does this IR tell you about structure?

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