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McMurry
www.cengage.com/chemistry/mcmurry
Chapter 19
Aldehydes and Ketones:
Nucleophilic Addition Reactions
Paul D. Adams University of Arkansas
Naming Ketones
Preparing Aldehydes
Oxidize primary alcohols using pyridinium chlorochromate
Alkenes with a vinylic hydrogen can undergo oxidative
cleavage when treated with ozone, yielding aldehydes
Reduce an ester with diisobutylaluminum hydride (DIBAH)
Preparing Ketones
Oxidize a 2 alcohol
Many reagents possible: choose for the specific
situation (scale, cost, and acid/base sensitivity)
Hydration of Aldehydes
Nu- approaches
75 to the plane of
C=O and adds to C
A tetrahedral
alkoxide ion
intermediate is
produced
Nucleophiles
Reactivity of Aromatic
Aldehydes
Base-Catalyzed Addition of
Water
Addition of water is
catalyzed by both
acid and base
The base-catalyzed
hydration nucleophile
is the hydroxide ion,
which is a much
stronger nucleophile
than water
Acid-Catalyzed Addition of
Water
Protonation of C=O
makes it more
electrophilic
Addition of HY to C=O
Uses of Cyanohydrins
Mechanism of Addition of
Grignard Reagents
Complexation of
C=O by Mg2+,
Nucleophilic
addition of R: ,
protonation by
dilute acid yields
the neutral
alcohol
Grignard
additions are
irreversible
because a
carbanion is not
a leaving group
Hydride Addition
Mechanism of Formation of
Imines
Imine Derivatives
Uses of Acetals
19.14 Spectroscopy of
Aldehydes and Ketones
Infrared Spectroscopy
Aldehydes and ketones show a strong C=O peak 1660 to
1770 cm1
aldehydes show two characteristic CH absorptions in the
2720 to 2820 cm1 range.
Aldehyde proton signals are near 10 in 1H NMR distinctive spinspin coupling with protons on the
neighboring carbon, J 3 Hz
C NMR of C=O
13
Mass Spectroscopy:
-Cleavage
Answer
The SN2 reaction of the OH ion on C6H5CHBr2
results in a very unstable bromoalcohol
intermediate. This intermediate quickly loses HBr
to give benzaldehyde.