Lec 4

1.
2 Aldehydes and Ketones

1.2.4 Reactions: Nucleophilic addition
Acetal formation
Many of the most interesting and useful reactions of aldehydes and ketones involve transformation of the initial product of
nucleophilic addition to some other substance under the reaction conditions. An example is the reaction of aldehydes with
alcohols under conditions of acid catalysis. The expected product of nucleophilic addition of the alcohol to the carbonyl group
is called a hemiacetal. The product actually isolated, however, corresponds to reaction of one mole of the aldehyde with two
moles of alcohol to give geminal diethers known as acetals:
Dr. Mudalungu/ Organic reactions 27

and functional group Chemistry
2022
1.2 Aldehydes and Ketones
Acetal formation
The overall reaction proceeds in two stages. The hemiacetal is formed in the first stage by nucleophilic addition of the alcohol
to the carbonyl group. The mechanism of hemiacetal formation is exactly analogous to that of acid-catalyzed hydration of
aldehydes and ketones.
Under the acidic conditions of its formation, the hemiacetal is

converted to an acetal by way of a carbocation intermediate:

2022
Acetal formation
This carbocation is stabilized by electron release from its oxygen

substituent:
Nucleophilic capture of the carbocation intermediate by an alcohol molecule leads to an acetal:
Self Exercise
Write a stepwise mechanism for the formation of benzaldehyde diethyl acetal from benzaldehyde and ethanol under
conditions of acid catalysis.
2022
Acetal formation is reversible in acid. An equilibrium is established between the reactants, that is, the carbonyl compound and
the alcohol, and the acetal product. The position of equilibrium is favorable for acetal formation from most aldehydes,
especially when excess alcohol is present as the reaction solvent. For most ketones the position of equilibrium is unfavorable,
and other methods must be used for the preparation of acetals from ketones.
Diols that bear two hydroxyl groups in a 1,2 or 1,3 relationship to each other yield cyclic acetals on reaction with either
aldehydes or ketones. The five-membered cyclic acetals derived from ethylene glycol are the most commonly encountered
examples. Often the position of equilibrium is made more favorable by removing the water formed in the reaction by azeotropic
distillation with benzene or toluene:

2022
Exercise: Write the structures of the cyclic acetals derived from each of the following.
(a) Cyclohexanone and ethylene glycol
(b) Benzaldehyde and 1,3-propanediol
(c) Isobutyl methyl ketone and ethylene glycol
(d) Isobutyl methyl ketone and 2,2-dimethyl-1,3-propanediol
Acetals are susceptible to hydrolysis in aqueous acid:

2022
Reaction with secondary amines: Enamines

Secondary amines are compounds of the type R2NH. They add to aldehydes and ketones to form carbinolamines, but their
carbinolamine intermediates can dehydrate to a stable product only in the direction that leads to a carbon–carbon double bond:
The product of this dehydration is an alkenyl-substituted amine,

or enamine.

2022
Example:
Write the structure of the carbinolamine intermediate and the enamine product formed in the reaction of each of the following:
(a) Propanal and dimethylamine, CH3NHCH3
Solution
Nucleophilic addition of dimethylamine to the carbonyl group of propanal produces a carbinolamine:
Dehydration of this carbinolamine yields the enamine:

2022
The wittig reaction

The Wittig reaction uses phosphorus ylides (called Wittig reagents) to convert aldehydes and ketones to alkenes.
Wittig reactions may be carried out in a number of different solvents; normally tetrahydrofuran (THF) or dimethyl sulfoxide
(DMSO) is used.

2022
The most attractive feature of the Wittig reaction is its regiospecificity. The location of the double bond is never in doubt. The
double bond connects the carbon of the original C=O group of the aldehyde or ketone and the negatively charged carbon of
the ylide.
Exercise
Solution for (a)

2022

Lec 4

Uploaded by

Copyright:

Available Formats

Lec 4

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Lec 4

Uploaded by

Copyright:

Available Formats

1.

2 Aldehydes and Ketones

Dr. Mudalungu/ Organic reactions 27

Under the acidic conditions of its formation, the hemiacetal is

Dr. Mudalungu/ Organic reactions 28

This carbocation is stabilized by electron release from its oxygen

Nucleophilic capture of the carbocation intermediate by an alcohol molecule leads to an acetal:

Dr. Mudalungu/ Organic reactions 30

Acetals are susceptible to hydrolysis in aqueous acid:

Dr. Mudalungu/ Organic reactions 31

Reaction with secondary amines: Enamines

The product of this dehydration is an alkenyl-substituted amine,

Dr. Mudalungu/ Organic reactions 32

Dehydration of this carbinolamine yields the enamine:

Dr. Mudalungu/ Organic reactions 33

The wittig reaction

Dr. Mudalungu/ Organic reactions 34

Dr. Mudalungu/ Organic reactions 35

You might also like