Fall 2005

Chapter 2: IR Spectroscopy
Analysis
Group Frequencies

CHMBD 449 Organic Spectral

Analysis
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IR Spectroscopy
III. Group Frequencies and Analysis
A. Introduction
1. When approaching any IR spectrum be sure to use the larger-tosmaller region approach- do not immediately focus on any one
single peak (even OH or C=O)
2.

From the Hookes Law derivation we are using we find that the
IR can be conveniently be divided into four major regions:
Bonds to H

Triple bonds

O-H
N-H
C-H

Double bonds Single Bonds

CC
CN

C=O
C=N
C=C

C-C
C-N
C-O
C-X
Fingerprint
Region

4000 cm-1

2700 cm-1

2000 cm-1

1600 cm-1

400 cm-1

IR Spectroscopy
III. Group Frequencies and Analysis
A. Introduction
3. If supporting information is available molecular formula,
chemical inferences (i.e. this was the product of an oxidation
reaction), assume this information is correct and the analysis of
the IR should support it (later in your careers you can doubt
information given to you)
4.

If a molecular formula is available, do an HDI!

5.

Many texts list various methods for approaching an IR spectrum;

use the method that works best for you and stick to it.

6.

The most common mistakes in spectral analysis are those of

jumping the gun to a conclusion (usually based on some small,
insignificant peak) or taking a random haphazard approach to
the spectrum (gee, here is an IR, oh, lets start looking for
phosphorus this time)
Be methodical, develop a scheme and stick to it!
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IR Spectroscopy
III. Group Frequencies and Analysis
Before we begin Each functional group will be described as follows:
Group
General What is most recognizable? What makes it different from
similar groups?
Group Frequencies (cm-1):
Bond
observe
d

in cm-1

type of vibration

Exceptions and things to

watch

Scale on bottom summarizes band positions and strengths

Strong Medium Weak -

IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkanes
General due to the small electronegativity difference between C
and H, hydrocarbon bands are of medium intensity at best and
give simple spectra
Group Frequencies (cm-1):
C-H

30002800

Stretch

-CH2-

~1465

Methylene bend
(scissor)

-CH3

~1375

Methyl bend (sym)

(CH2)4-

~720

Rocking motion 4 or
more CH2- (long chain
band)

C-C

Strained ring systems may

have higher

Not interpretively
useful, small weak
peaks

IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkanes Dodecane C12H26

IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkanes Cyclopentane C5H10

IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkanes
Additional If the 1400-1350 region is free of interference, the
presence of certain alkyl groups can be discerned:
Methylene

Methyl

H
C

C
H

H
Scissor
1465

Bendasymm
1450

usually overlap

Bendsymm
1375
C

1380

1370

CH3
CH3 gem-dimethyl
CH3

1390

1370

CH3

t -butyl

CH3

IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkanes
Additional Example: Compare 2,2-dimethylpentane vs. 2-methylhexane:

vs.

IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkenes
General slightly more complex than alkanes; asymmetric C=C is
observed as well as the sp2-C-H stretch. Still, bands are weak to
medium in intensity
Group
Frequencies
(cm-1):
=C-H
3095Stretch
3010

- Diagnostic for unsaturationmay be aromatic as well

=C-H

1000-650 Out-of-plane (oop)

bend

- Can be used to determine

degree of substitution

C=C

16601600

- Can be reduced by resonance

- Symmetrical C=C do not
absorb
- trans- weaker than cis-

Stretch

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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkenes 1-octene C8H16
Note you still have alkane present!

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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkenes trans-4-octene C8H16
Note absence of C=C band, shouldering of C-H band

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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkenes cis-2-pentene C5H10
Note shouldering of C-H band

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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkenes cyclopentene C5H8

Note increased complexity due to ring vibrations

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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkenes
Substitution The out of plane =C-H bend produces strong bands
but interference can come from aromatic rings (similar oop) and
C-Cl bonds (~700)
1000
900
800
700
monosubstituted
R
cis-1,2
R

trans-1,2

R
R

1,1-disubstitued
R

trisubstituted
R

tetrasubstituted

none, with weak C=C

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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkenes
Substitution The monosubstitued band is very reliable; and the
variance induced by electronic effects is observed
1000

monosubstituted (R-)
monosubstitued
w/lone pair group
(ex. Cl, -F, -OR)
monosubstitued
w/conj. group
(ex. C=O, CN)

900

800

700

overtone usually observed

The shifts are similar for 1,1-disubstitued systems

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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkenes
Rings Incorporation of a double bond endocyclic or exocyclic to
a ring may shift the observed band
Endocyclic: Ring strain shifts the C=C band to lower (ex.
cyclopropene)

C=C 1650

1646

1611

1566

1656

The adjacent C-C bond couples with the C=C system if the
resulting component vector is along the line of the C=C bond an
increase in occurs this reaches a minima at 90o for
cyclobutene (no net component along C=C bond) and rises
again with cyclopropene
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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkenes
Rings
Endocyclic: If C=C at a ring fusion, absorption is reduced as if
one further carbon was removed from the ring:
C=C 1611
The presence of additional alkyl groups on the ring dramatically
raises C=C
R

C=C 1656

1788

1641

1883

C=C 1566

1675
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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkenes
Rings
Exocyclic: these C=C bonds give an increase in absorption with
decreasing ring size:

C=C 1940

1780

1678

1657

1651

As the angle between the two C-C bonds is reduced more p

character is required (sp = 180, sp2 = 120, sp3 = 109.5,
sp>3 = <109
The p character of the double bond is reduced, but the stronger
bond is strengthened to a greater degree
Think of the allene example (2-membered ring) as an extreme
example
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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkynes
General can be symmetric, psuedo-symmetric or internal greatly
reducing the number of observed bands
Group Frequencies (cm-1):
C-H

~3300

Stretch

- Diagnostic for terminal alkyne

CC

~2150

Stretch

- Can be reduced by resonance

-Symmetrical and psuedo-sym.
CC do not absorb

C-H

900-700

Bend

(Text does not list)

Possible not to observe any
bands for the CC system

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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkynes 1-hexyne C6H10

HC C

Nice terminal, asymmetric, well behaved alkyne

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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkynes 3-hexyne C6H10

C C

A not-so-nice, internal, symmetrical alkyne

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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Alkynes 1-hexyne C6H10

HC C

Nice terminal, asymmetric, well behaved alkyne

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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Mononuclear aromatic rings
General not true alkenes; most of the small bands associated with
them are not of diagnostic value; electronic effects of a single
group on the ring can change the observed bands drastically
Group Frequencies (cm-1):
-C-H

30503010

Stretch

Also for alkenes

C-H

900-690

Out of plane (oop) bend

Can be used to determine

substitution pattern

20001667

Overtone and combination

bands

If observed, similar too oop

16001400

Ring stretch observed as

two doublets (1600, 1580,
1500 & 1450)

Greatly dependent on
substituents

=C-H

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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Mononuclear aromatic rings toluene C7H8

CH3

Typical mono-substituted (EDG) ring

25

IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Mononuclear aromatic rings o-xylene C8H10

CH3
CH3

Typical ortho-substituted (EDG) ring

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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Mononuclear aromatic rings m-xylene C8H10
Typical meta-substituted (EDG) ring

CH3

CH3

27

IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Mononuclear aromatic rings p-xylene C8H10
Typical para-substituted (EDG) ring

CH3

CH3

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IR Spectroscopy
III. Group Frequencies and Analysis
H2C
CH3
B. The Hydrocarbons
C
Mononuclear aromatic rings -methylstyrene C9H10
Conjugated mono-substituted ring

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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Mononuclear aromatic rings
Substitution The aromatic out of plane =C-H bend produces strong
bands but interference can come from alkenes (similar oop) and
C-Cl (~700)
Consider this region to only be reliable for alkyl-, alkoxy-, halo-,
amino-, and acetyl substituted rings
Interpretation is often unreliable for nitro-, carboxylic- and
sulfonic groups
The overtone of these bands is the dominant source of the
combination and overtone bands observed at 2000-1667

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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Mononuclear aromatic rings
Substitution
900

800

700

600

mono
ortho
meta
para
1,2,4
1,2,3
1,3,5

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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Mononuclear aromatic rings
Substitution The aromatic combination and overtone bands are a
set of weak absorptions that occur from 2000-1667. This is
often obscured by C=O
The general shape of
the pattern is used for
determining
substitution pattern;
typically only a neat
liquid sample gives
an intense enough set
of bands for analysis

mono
ortho
meta
para
1,2,3
1,3,5
1,2,4

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IR Spectroscopy
III. Group Frequencies and Analysis
B. The Hydrocarbons
Polynuclear and Hetero- aromatic rings
General All bands for these aromatic systems are similar to the
mononuclear systems; shifts should be assumed, and analysis
would be case-by-case
N
N
N
S

H
S
O

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IR Spectroscopy
III. Group Frequencies and Analysis
C. sp3 Oxygen Alcohols, phenols and ethers
Alcohols
General the best recognized group on carefully selected spectra,
but H-bonding effects can drastically change the position,
intensity and shape of the O-H band
Group Frequencies (cm-1):
O-H

36503600

Stretch

Seen in dilute solution or

gas phase spectra

34003300

Stretch

The classic H-bonded

band, seen in addition to the
free band in solution

C-O-H

14401220

Bend

Often obscured by -CH3 bend

C-O

12601000

Stretch

Can be used to determine

1o, 2o, 3o or phenolic
structure

(free)

O-H
(Hbond)

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IR Spectroscopy
III. Group Frequencies and Analysis
C. sp3 Oxygen Alcohols, phenols and ethers
HO
Alcohols 1-octanol
Neat liquid sample gives classic spectrum

35

IR Spectroscopy
III. Group Frequencies and Analysis
C. sp3 Oxygen Alcohols, phenols and ethers
HO
Alcohols 1-octanol
Same sample in dilute CCl4 solution (solvent bands deleted for
clarity)

36

IR Spectroscopy
III. Group Frequencies and Analysis
C. sp3 Oxygen Alcohols, phenols and ethers
Phenols p-cresol

OH

Presence of aromatic bands, sharper -OH

37

IR Spectroscopy
III. Group Frequencies and Analysis
C. sp3 Oxygen Alcohols, phenols and ethers
Alcohols
Substitution Using the position of the C-O stretching band, it is
possible to suggest a 1o, 2o, 3o or phenolic structure to the
alcohol; but these should be considered as base values, that
may be changed by the effects of conjugation
or an adjacent
OH
ring system
base value
phenol
1220
tertiary

1150

secondary 1100

OH
OH

C-O
1070

C-O
1070

C-O
1017
OH
HC

OH

primary

1050

C-O
1060

C-O
1030

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IR Spectroscopy
III. Group Frequencies and Analysis
C. sp3 Oxygen Alcohols, phenols and ethers
Ethers
General like alkynes, the simplicity of the spectra may allow them
to pass unnoticed deduce from molecular formula if one should
be present
Group Frequencies (cm-1):
C-O

13001000

Stretch (asymm.)

Absence of C=O and O-H

will confirm it is not ester or
alcohol
Simple alkyl ethers usually
one band at 1120, aryl alkyl
ethers give two bands
1250 & 1040

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IR Spectroscopy
III. Group Frequencies and Analysis
C. sp3 Oxygen Alcohols, phenols and ethers
Ethers diispropyl ether

Spectrum dominated by all other functionality

40

IR Spectroscopy
III. Group Frequencies and Analysis
C. sp3 Oxygen Alcohols, phenols and ethers
Ethers
Additional Types
Aryl and vinyl ethers The effect of conjugation gives the C-O bond
a small amount of double bond character, raising the observed
H2C

C
H

H2C

C
H

Furthermore, strongly asymmetric systems (aryl alkyl and vinyl

alkyl ethers) may show an additional weak C-O band for the
symmetric stretch at 1040 and 850 respectively

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IR Spectroscopy
III. Group Frequencies and Analysis
C. sp3 Oxygen Alcohols, phenols and ethers
Ethers
Additional Types
Epoxides Most important bands are the ring deformation bands at
asym 950-815 and sym 880-750
Weaker breathing mode band is present at 1280-1230
O

Acetals and Ketals Give four or five unresolved bands in the 12001020 region
R

O
R

R
O

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IR Spectroscopy
III. Group Frequencies and Analysis
C. sp3 Nitrogen Amines
Amines
General Once presence is determined, the substitution at nitrogen
is easy to determine; only the 3 amine may present a problem
Group Frequencies (cm-1):
N-H

36503600
(2 bands)
16401560

Stretch (sym. and

asym.)

34003300
(1 band)
1500

Stretch

N-H

~800

Oop bend

N-N

13501000

Stretch

(-NH2)

N-H
(-NHR)

Bend

Bend

For alkyl amines, very weak

for aromatic 2 amines,
stronger

Remember 3 amines have

no N-H bands

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