Scribd
Upload
20 views26 pages

Aldehydes and Ketones: Reactivity and Mechanisms

Chapter 9 of 'Organic Chemistry for Medical Students' discusses aldehydes and ketones, highlighting their structures, reactivity, and electrophilicity. It explains that aldehydes are generally more reactive than ketones due to their less crowded transition states and provides insights into nucleophilic addition reactions, particularly cyanohydrin formation. The chapter also covers oxidation reactions, noting that aldehydes are more easily oxidized than ketones, which can be demonstrated through the Tollens’ silver mirror test.

Uploaded by

zenitsuhassouneh
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
20 views26 pages

Aldehydes and Ketones: Reactivity and Mechanisms

Chapter 9 of 'Organic Chemistry for Medical Students' discusses aldehydes and ketones, highlighting their structures, reactivity, and electrophilicity. It explains that aldehydes are generally more reactive than ketones due to their less crowded transition states and provides insights into nucleophilic addition reactions, particularly cyanohydrin formation. The chapter also covers oxidation reactions, noting that aldehydes are more easily oxidized than ketones, which can be demonstrated through the Tollens’ silver mirror test.

Uploaded by

zenitsuhassouneh
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPT, PDF, TXT or read online on Scribd

Organic Chemistry for Medical Students

101115
Chapter 9
Aldehydes and Ketones
Draw the structure for the followings
1.m-bromobenzaldehyde 2. isopropyl methyl ketone
3. 2-pentanone 4. cylcohexanecarbaldehyde
5. 3-pentyne-2-one
8
Relative Reactivity of Aldehydes and
Ketones
 Aldehydes are generally more reactive than ketones in
nucleophilic addition reactions
 The transition state for addition is less crowded and lower
in energy for an aldehyde (a) than for a ketone (b)
Aldehydes have one large substituent bonded to the C=O:
ketones have two

10
Electrophilicity of Aldehydes and
Ketones
Aldehyde C=O is more polarized than ketone C=O
As in carbocations, more alkyl groups stabilize + character
Ketone has more alkyl groups, stabilizing the C=O carbon
inductively

11
Reactivity of Aromatic Aldehydes
Less reactive in nucleophilic addition reactions than aliphatic
aldehydes
Electron-donating resonance effect of aromatic ring makes
C=O less reactive electrophilic than the carbonyl group of an
aliphatic aldehyde

12
Rank the following in decreasing order of reactivity:

O
O
H O
H O
H
H

N
OCH3 O
O

13
Nucleophilic Addition of HCN: Cyanohydrin
Formation
Aldehydes and unhindered ketones react with HCN to yield
cyanohydrins, RCH(OH)CN

Cyanohydrin formation is somewhat unusual because it is one of the few examples


of the addition of a protic acid (H-Y) to a carbonyl group. As noted in the previous
section, protic acids such as H2O, HBr, HCl, and H2SO4 don't normally yield carbonyl
addition products because the equilibrium constants are unfavorable. With HCN,
however,
17 equilibrium favors the cyanohydrin adduct.
Mechanism of Formation of
Cyanohydrins
Addition of HCN is reversible and base-catalyzed, generating
nucleophilic cyanide ion, CN
Addition of CN to C=O yields a tetrahedral intermediate,
which is then protonated
Equilibrium favors adduct

18
O OCH3
CH3OH (excess)
C H C H
H+ (catalyst)
OCH3
OH
O
1. CH3CH2MgBr
CH3CH2CCH2CH3
CH3CH2CCH2CH3
2. H2O, H+
CH2CH3

**Show how the following alcohol can be synthesized from a Grignard reagent
and a carbonyl alcohol:

OH

C CH3

1. CH3MgBr
H
2. H2O, H+
  1- LiAlH4
OH
C O C
2- H2O/ H+
H
cyclohexanone
cyclohexanol

O OH
1. LiAlH4
H3C CH CH3CH2
2. H3O+

O
1. LiAlH4
C CH3
2. H3O+
•
Oxidation of carbonyl Compounds
Aldehydes are more easily oxidized than ketones. Oxidation of an aldehyde gives an acid with the same number of carbon
atoms. Since the reaction occurs easily, many oxidizing agents, such as KMnO4, CrO3, AgO2, and peracids, will work.
• A laboratory test that distinguishes aldehydes from ketones takes advantage of their different ease of oxidation. In the
Tollens’ silver mirror test, the silver-ammonia complex ion is reduced by aldehydes to metallic silver.

• 1

• 2

• 3
O O
+
CrO3, H
H3C(H2C)5 C H H3C(H2C)5 C OH
(Jones' reagent)

O O

H Ag2O
OH

O O
R C H 2 Ag(NH3)2 3 OH R C O
acide anion
aldehyde silver-ammonia
complex ion
(colorless) 2 Ag 4 NH3 H2O
silver mirror

You might also like