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Aldehydes and Ketones

O O O O
C C C C
H H R H R R'
carbonyl formaldehyde aldehydes ketones
group

O O
O
H H
H
HO
OCH3
cinnamaldehyde
vanillin
geranial
OH OH

O HO
testosterone estradiol
(male sex hormone or androgen) (female sex hormone or estrogen)
[4 tons of sow ovaries 0.012 g]

progesterone
(controls ovulation
during pregnancy)

O
Introduction
Aldehydes are compounds of the general
formula RCHO; Ketones are compounds of
the general formula RRCO. the group R
and R may be aliphatic or aromatic. In one
aldehyde, HCHO, R is H).
Introduction
Both aldehydes and ketones contain carbonyl
group, C=O, and are often referred to
collectively as carbonyl compounds. It is the
carbonyl group that largely determines the
chemistry of aldehydes and ketones.
The different in structure affects their properties
in two ways:
a) Aldehydes are quite easily oxidized, whereas
ketones are oxidized only with difficulty.
b) Aldehydes are usually more reactive than
ketones toward nucleophilic addition, the
characteristic reaction of carbonyl compounds.
Structure

sp2O -O O O
R
C O
R +C C C
R R R R R R
(sp2C + sp2O)
(sp3C + sp2C) electrophilic carbon

-larger dipole (looser electrons),


more polar than ethers or alcohols
-more soluble than ethers
-less soluble than alcohols (no H-bonding)
Nomenclature of Aldehydes
The IUPAC names of aldehydes follow the usual
pattern.
The longest chain carrying the CHO group is
considered the parent structure and is named by
replacing ane of the corresponding alkane by al.
the position of a substituent is indicated by a
number, the carbonyl carbon always being
considered as C-1.
Nomenclature of Aldehydes
A. IUPAC
1. alkanal (aldehyde carbon always #1)

O
3-methylbutanal
H
O

H trans-3-phenyl-2-propenal (cinnamaldehyde)

H
(E)-3,7-dimethyl-2,6-octadienal (geranial)
Nomenclature of Aldehydes
A. IUPAC
2. cyclic aldehydes
O
cyclopentanecarbaldehyde
H

H
m-nitrobenzenecarbaldehyde
m-nitrobenzaldehyde

NO2
Nomenclature of Aldehydes
B. Common names
O
methanal (formaldehyde)
H H
O
ethanal (acetaldehyde)
H
O
propanal (propionaldehyde)
H
O
butanal (butyraldehyde)
H
O
2-methylpropanal (isobutyraldehyde)
H
Nomenclature of Ketones
The IUPAC names of aldehydes follow the usual
pattern.
The longest chain carrying the C=O group is
considered the parent structure and is named by
replacing ane of the corresponding alkane by
one. the position of a substituent is indicated by a
number, the carbonyl carbon always being
considered given the lowest possible number.
Nomenclature of Ketones
A. IUPAC
alkanone (carbonyl carbons gets lowest number)

O
4-methyl-2-pentanone

1-phenyl-1-propanone (propiophenone)

2-isopropyl-5-methylcyclohexanone
Nomenclature of Ketones
B. Common names
O
alkyl alkyl' ketone
R R'

O
propanone (dimethyl ketone, acetone)

O
butanone (methyl ethyl ketone, MEK)

O
4-methyl-2-pentanone (methyl isobutyl ketone, MIBK)

O
3-buten-2-one (methyl vinyl ketone, MVK)
Nomenclature of Ketones
B. Common names
O

R phenones

1-phenylethanone (acetophenone)

1-phenyl-1-propanone (propiophenone)

diphenylmethanone (benzophenone)
Nomenclature of Aldehydes and Ketones
A. IUPAC
3. priority: aldehyde > ketone > alcohol
O
5-hydroxy-2-hexanone

OH
O

H
4-hydroxy-3-methoxybenzaldehyde
HO (vanillin)
OCH3
O
O
2-oxocyclopentanecarbaldehyde
H
Preparation of Aldehydes and
Ketones
Ozonolysis

The addition of ozone, O3, to alkenes is followed


by the introduction of Zn and acid to produce
carbonyl compound; aldehydes and ketones.
Examples of Ozonolysis Reaction
Examples of Ozonolysis Reaction
Ozonolysis of cyclic alkenes
Oxidation of Alcohols
General equation:
Oxidation of Alcohols

KMnO4, H2Cr2O7, K2Cr2O7


Oxidation of Alcohols
Examples:
Reactions of Aldehydes and
Ketones
Reactions of Aldehydes and Ketones:
Nucleophilic addition
base-promoted:
O O OH
H+
C C C
Nu Nu
Nu

acid-catalyzed:
H OH OH
O H+ O
-H+
C C
C C
HNu Nu
HNu
Oxidation of Carbonyl Compounds
Aldehydes are oxidized to carboxylic acids.
Ketones are difficult to be oxidized.

KMnO4 @ K2Cr2O7 @ Ag(NH3)2+


R-CHO @ Ar-CHO RCOOH @ Ar-COOH

Used chiefly for detection of aldehydes


Oxidation of Carbonyl Compounds
I. Oxidation of aldehydes

O O
[O]
C C
R H R OH

[O] = CrVI MnVII


CrO3 KMnO4
K2Cr2O7

some aldehydes very easily oxidized:


O O

H O2 OH
(air)
Reduction of Carbonyl
Compounds
Reduction of Carbonyl Compounds to
Alcohols

Aldehydes are reduced to primary alcohol.


Ketones are reduces to secondary alcohol.
Reduction of Carbonyl Compounds to
Alkanes
O O
Zn(Hg)/HCl
R-C-R' @ R-C-H R-CH2-R' @ RCH3
Clemensen Reduction

O O
NH2NH2/KOH
R-C-R' @ R-C-H R-CH2-R' @ RCH3
Wolf-Kishner Reduction
Reduction of Carbonyl Compounds to
Alkanes
Examples:

O
NH2NH2, Base

Cyclopentanone Cyclopentane

Zn(Hg), HCl
CH3CH2CH2COCl, Base

AlCl3

Benzene n-Butylbenzene
n-Butyrophenone @
Phenyl n-propyl ketone
Addition of Grignard Reagents to Aldehydes
and Ketones: Synthesis of Alcohols
General equation
Reaction of GR With Formaldehyde

H2 O @ H3 O+

Example

Note: you are strongly


encouraged to refer back for this
particular sub-chapter in
Alcohol's Note for details.
Reaction of GR With Higher Aldehydes

Example

Note: you are strongly encouraged to


refer back for this
particular sub-chapter in Alcohol's Note
for details.
Reaction of GR With Ketones

Example

Note: you are strongly encouraged to refer back for this


particular sub-chapter in Alcohol's Note for details.
Addition of Water/Hydration

Geminal diol is not stable.


It is in equilibrium with the carbonyl compound.
Most of aldehydes and ketones do not react with water.
Only formaldehyde (HCHO) forms stable geminal diol.

H
+ H-OH H H
OH
H O
OH
End of Chapter

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