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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
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
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
H O H O
H C R R
O
H O H O
H weaker weaker
bond bond
O O
Infrared Spectroscopy
Carbonyl Compounds
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
O R
R O
s-cis s-trans
Infrared Spectroscopy
Carbonyl Compounds
1-penten-2-one
C=C
C=O
Infrared Spectroscopy
Carbonyl Compounds
O O O O
O O
O O
NH NH
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
O O
δ-
X X
δ+ δ-
δ+
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
methyl chloroacetate
O
Cl
OCH3
C=O
Infrared Spectroscopy
Carbonyl Compounds
4. Internal Hydrogen-Bonding
• effects can be additive
O O
OMe OMe
OMe OH
• 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
Infrared Spectroscopy
Aldehydes
octanal
Infrared Spectroscopy
Aldehydes
crotonaldehyde
Infrared Spectroscopy
Ketones
cyclohexanone
overtone
C=O
Infrared Spectroscopy
Ketones
mesityl oxide
H
O O O O
Infrared Spectroscopy
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)
Infrared Spectroscopy
Carboxylic Acids
isobutyric acid
Infrared Spectroscopy
Carboxylic Acids
OH
1-octanol
OH
Infrared Spectroscopy
O O
Carboxylic Acids R O R O
sodium benzoate
O- +Na
symmetric asymmetric
stretch stretch
Infrared Spectroscopy
Esters
- conjugation with ester oxygen moves band to higher frequencies (15-25 cm-1)
R O
ethyl acetate
OCH2CH3
C=O
C-O
1743 cm-1
Infrared Spectroscopy
Esters
methyl benzoate
1724 cm-1
Infrared Spectroscopy
O O
Esters R O R O
phenylacetate
C=O C-O
1765 cm-1
Infrared Spectroscopy
Esters
effect of effect of
ring size effects α,β-conjugation conjugation with O
O O O
O O O
O O O
O O O
O
1820 cm-1
Infrared Spectroscopy
Amides
O O O
H H R
R N R N R N
H R R
1° 2° 3°
Infrared Spectroscopy
Amides
isobutylamide
NH2
NH2 C=O
Infrared Spectroscopy
Amides
N-methylacetamide
Infrared Spectroscopy
Amides
N,N-dimethylacetamide
O
CH3
N
CH3
Infrared Spectroscopy
Amides
O
O
O
NH
NH
NH
benzoyl chloride
Infrared Spectroscopy
Acid Anhydrides
propionic anhydride
Infrared Spectroscopy
Imines, Oximes, and Hydrazones
R' OH NR'2
N N N
R R R R R R
imine oxime hydrazone
http://www.ochemonline.com/Infrared_spectroscopy_absorption_table
Infrared Spectroscopy
Imines, Oximes, Hydrazones
2-butanone oxime
OH
N
C=N
N-OH (1665 cm-1)
Infrared Spectroscopy
Imines, Oximes, Hydrazones
acetone dimethylhydrazone
NMe2
N
C=N
benzaldehyde phenylhydrazone
H
N
N Ph
N-H
C=N
(1602, 1593 cm-1)
Infrared Spectroscopy
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
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
cyclohexanecarbonitrile
C≡N
o-tolunitrile
C≡N
Infrared Spectroscopy
Isocyanate and Isothiocyanate
butyl isocyanate
N=C=O
cyclohexane isothiocyanate
N=C=S
Infrared Spectroscopy
Azides and Carbodiimides
ethyl 2-azidoisovalerate
N3
N,N’-dicyclohexylcarbodiimide
N=C=N
Infrared Spectroscopy
Allenes
1,2-pentadiene
H H
C C C
CH3CH2 H
sp2 C-H
C=N
N-OH C=C=C
Infrared Spectroscopy
Other Groups
R F R Cl R Br R I
R NO2 Ar NO2 R SH
iodoform
I
H C I
I
C-I
stretch
Infrared Spectroscopy
Halides
chloroform
chloroform-d
C-D Cl
D C Cl
Cl
Infrared Spectroscopy
Nitro Compounds
2-nitropropane
O O
N
NO2
Infrared Spectroscopy
Thiols
butanethiol
S-H
Infrared Spectroscopy
What Can the IR Tell You?
- 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.)
- 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.
Infrared Spectroscopy
Practice Problem 1
C8H12O
Infrared Spectroscopy
Practice Problem 1
C9H10O