1. 22 22-1 Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved. Introduction to Organic Chemistry 2 ed William H. Brown

2. 22 22-2 Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved. Infrared Spectroscopy Chapter 22

3. 22 22-3 Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved. Infrared Spectroscopy The IR region covers 7.8 x 10 -7 m (just above the visible region) to 2.0 x 10 -3 m (just below the microwave region) Organic chemistry uses mainly the vibrational IR, which covers 2.5 x 10 -6 m (2.5  m) to 2.5 x 10 -5 m (25  m) absorption of IR radiation in this region causes bonds to change from a lower vibrational energy level to a higher one

4. 22 22-4 Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved. Infrared Spectroscopy The frequency of IR radiation is commonly expressed in wavenumbers WavenumberWavenumber: the number of waves per centimeter, cm -1 (read reciprocal centimeters) the vibrational IR extends from 4000 cm -1 to 400 cm -1

5. 22 22-5 Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved. Infrared Spectroscopy For the IR spectra recorded in this text, calibrations are

6. 22 22-6 Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved. Molecular Vibrations Atoms joined by covalent bonds undergo continual vibrations relative to each other the energies associated with these vibrations are quantized; within a molecule, only specific vibrational energy levels are allowed the energies associated with transitions between vibrational energy levels for most covalent bonds are from 2 to 10 kcal/mol (8.4 to 42 kJ/mol)

7. 22 22-7 Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved. Molecular Vibrations For a molecule to absorb IR radiation, the frequency of radiation must match the frequency of a bond vibration the bond undergoing vibration must be a polar bond the greater the polarity of the bond, the more intense the absorption Covalent bonds which do not meet these criteria are said to be IR inactive the C-C double and triple bonds of symmetrically substituted alkenes and alkynes, for example, do not absorb IR radiation because they are not polar bonds

8. 22 22-8 Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved. Molecular Vibrations For a nonlinear molecule containing n atoms, there are 3n -6 allowed fundamental vibrations thus, for even a relatively small molecule, a large number of vibrational energy levels exist and patterns of IR absorption can be very complex The simplest vibrational motions are bending and stretching

9. 22 22-9 Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved. Correlation Tables Characteristic IR absorptions for the types of bonds and functional groups we deal with most often

10. 22 22-10 Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved. Correlation Tables Alkanes and alkenes

11. 22 22-11 Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved. Correlation Tables Alcohols and ethers Aromatic rings

12. 22 22-12 Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved. Correlation Tables Amines

13. 22 22-13 Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved. Correlation Tables Aldehydes and ketones because few other bond vibrations absorb energy in this region, a peak here is a reliable means of confirming the presence of a C=O group the C=O group, however, may also be that of a carboxylic acid, anhydride, or ester

14. 22 22-14 Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved. Correlation Tables Acids, esters, and amides

15. 22 22-15 Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved. End Chapter 22 InfraredSpectroscopy