Chapter 12, MS and IR 1

Chapter 12 Infrared Spectrophotometry

Chapter 12, MS and IR 2

The IR Experiment
Stretching Vibrations
Atompositions with respect to each other are not fixed !! There are relative movements to each other, which can be described by a spring-model. Considering two atoms results in the following model

Energy-uptake can be accomplished by electromagnet radiation

Stretching and Bending Vibrations of three atoms

a)stretching:

Asymmetrical stretching

as

Symmetrical stretching

Chapter 12, MS and IR 3

In-plane bending (scissoring)

Out-of-plane bending (wagging)

Out-of-plane bending (twisting)

In-plane bending (rocking)

Stretching Frequencies as a function of Atomic Weight: C-H 3200-2800 cm-1 C-O 1200-1050 cm-1 C-Cl 800-650 cm-1

Chapter 12, MS and IR 4

Stretching Frequencies as a function of Bond Strengths

Bond Frequency (cm-1)

CH2 C C

2960 (as), 2870 (s) 3020

H
C C H

3300

1675-1650 2140-2100 1140-1070 1715

CH2
C

O
O

Chapter 12, MS and IR 5

Symmetry is an important factor of IRspectra since it is associated with an oscillating electric dipole. Ring strain
The effect of ring strain can be easily observed in IR:

O O

Carbonyl-frequency: 1714 cm-1 1746 cm-1

1783 cm-1

C=C stretching: 1649 cm-1 1656 cm-1

1677 cm-1

Chapter 12, MS and IR 6

Stereoisomers: trans-substituted alkenes : strong band at ~ 970 cm-1 cis-substituted alkenes : medium bands at 730 cm 1 and 650 cm-1 Conformational Isomers:
O Cl H
carbonyl : 1745 cm-1 1725 cm-1

O H Cl

Chapter 12, MS and IR 7

IR Spectra of Alcohols
CH3CH2OH

CH 3 CH3 C CH 2 CH 3

CH3 CH CH2OH

A: O-H B: C-H C: CH2-vibration D: C-O stretch

Chapter 12, MS and IR 8

IR Spectra of Ketones
O CH3 C CH3

Chapter 12, MS and IR 9

O CH3 C CH2CH2CH3

A, B, C: C-H D: C=O E,F,G: CH2-vibration

IR Spectra of Alkenes
H2C CH(CH2)7CH3

A: C-H aliphatic B: C-H olefinic C: C=C stretch D: =CH out of plane and CH2

Chapter 12, MS and IR 10

IR Spectra of Alkynes
HC CH(CH2)3CH3

A, C, E, due to alkyne: A: C-H alkyne C: CC stretch alkyne E: CCH bend alkyne

Chapter 12, MS and IR 11

IR Spectra of Aromatic Compounds

OH

A: O-H B: C-H C: Overtones D: C=C aromatic ring stretch

CH2OH

Chapter 12, MS and IR 12

CH3 CH3

Aromatic Overtone and Combination Bands

Chapter 12, MS and IR 13

IR Spectra of Amines
N-H stretch of 1o amines: doublet at 3500, 3400 cm-1 (very diagnostic but weak in intensity) N-H stretch of 2o amines: 3310-3350 cm-1 (weak) N-H bend of 1o amines: 1580-1650 cm-1 (medium to strong) N-H wagging of 1o or 2o amines: 666-909 cm-1 (medium to strong, usually broad) CH3(CH2)6CH2NH2

Chapter 12, MS and IR 14

Summary of IR Stretching Frequencies

Frequency Functional Group (cm-1) 3300 O H alcohol amine, N H amide alkyne C H 3000 alkane C H Comments always broad may be broad, sharp, or broad with spikes always sharp just below 3000 cm-1

alkene

C H

just above 3000 cm-1

acid 2200 1710 (very strong) 1600-1700 alkene alkyne nitrile carbonyl

C O
C C C N

very broad
H

just below 2200 cm-1 just above 2200 cm-1 ketones, aldehydes, acids, esters higher (1735 cm-1) amides lower; conjugation (1650 cm-1) aromatic lower; conjugation (1600 cm-1) stronger than C=C stronger than C=C (see above)

imine

amide 1000-1200 ether ester alcohol

Chapter 12, MS and IR 15