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20.8 Spectroscopy of Carboxylic Acids and Nitriles

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    90988

    • Objectives

    After completing this section, you should be able to

    1. identify the two characteristic infrared absorptions displayed by all carboxylic acids.
    2. state the approximate 1H NMR absorption of a carboxylic acid proton.
    3. use infrared and NMR spectroscopy data to assist in the identification of an unknown carboxylic acid, with or without the assistance of a table of characteristic absorptions.

    IR

    The carboxyl group is associated with two characteristic infrared stretching absorptions which change markedly with hydrogen bonding. The spectrum of a CCl4 solution of propionic acid (propanoic acid), shown below, is illustrative. Carboxylic acids exist predominantly as hydrogen bonded dimers in condensed phases. The O-H stretching absorption for such dimers is very strong and broad, extending from 2500 to 3300 cm-1. This absorption overlaps the sharper C-H stretching peaks, which may be seen extending beyond the O-H envelope at 2990, 2950 and 2870 cm-1. The smaller peaks protruding near 2655 and 2560 are characteristic of the dimer. In ether solvents a sharper hydrogen bonded monomer absorption near 3500 cm-1 is observed, due to competition of the ether oxygen as a hydrogen bond acceptor. The carbonyl stretching frequency of the dimer is found near 1710 cm-1, but is increased by 25 cm-1 or more in the monomeric state. Other characteristic stretching and bending absorptions are marked in the spectrum.

    Nitriles show a distinctive absorption for the C-N triple bond which appear near 2250 cm-1

    Figure IR17. IR spectrum of benzonitrile. Source: SDBSWeb : http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology of Japan, 14 July 2008)

    NMR

    The combination of anisotropy and electronegativity causes the O-H hydrogen in a carboxylic acid to be very deshielded.

    Hydrogen environments adjacent to a carboxylic acid are shifted to the region of 2.5-3.0 ppm.Deshielding occurs due to the fact that the sp2 hybridized carbon the the carboxylic acid is more electronegative than a sp3 hybridized carbon.