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Chapter 17: Aldehydes and Ketones. Nucleophilic Addition to C=O



Summary | Aldehydes and Ketones | Preparations of Aldehydes and Ketones | Reactions of Aldehydes and Ketones | Spectroscopic Analysis of Ethers | Self Assessment | Quiz |


Aldehydes and Ketones

Chapter 17: Aldehydes and Ketones. Nucleophilic Addition to C=O

Nomenclature:
Aldehydes: functional group suffix = -al (review)
Ketones: functional group suffix = -one (review)
Functional group prefix = oxo-
 
 

methanal
ethanal
propanone

Physical Properties:

The implications of these effects are: Structure:
methanal
ethene
propanone

 

Reactivity:

electrostatic potential of methanal The image shows the electrostatic potential for methanal (formaldehyde)
The more red an area is, the higher the electron density and the more blue an area is, the lower the electron density. 
  • The O atom in the C=O is a region of high electron density (red) due to the lone pairs.
  • The carbonyl oxygen atoms are Lewis bases (site of protonation)
  • There is low electron density (blue) on the C atom of the C=O group.
electrostatic potential for propanone The image shows the electrostatic potential for propanone (acetone). 
The more red an area is, the higher the electron density and the more blue an area is, the lower the electron density. 
  • The O atom in the C=O is a region of high electron density (red) due to the lone pairs.
  • The carbonyl oxygen atoms are Lewis bases (site of protonation)
  • There is low electron density (blue) on the C atom of the C=O group

 
IMPORTANT : The reactivity of aldehydes and ketones can be easily rationalized by considering the important resonance contributor which has a +ve C and -ve O. 
Note that this matches the ideas shown in the electrostatic potential diagrams shown above.
resoance in a ketone

 
 
In general the reactivity order towards nucleophiles is as shown to the right : aldehydes > ketones
The substituents have two contributing factors 
  1.  Size of the substituents attached to the C=O. Larger groups sterically hinder the approach of the Nu.
  2. The electronic effect of the substituent. Alkyl groups are weakly electron donating so they make the C in the carbonyl less electrophilic.
relative reactivity order towards nucleophiles

You can look at the accessible effect in the following series of aldehydes and ketones:
 

methanal
ethanal
propanone
di-t-butyl ketone
L button highlights E+ center, R button resets


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