Академический Документы
Профессиональный Документы
Культура Документы
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
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
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.
O O
[O]
C C
R H R OH
H O2 OH
(air)
Reduction of Carbonyl
Compounds
Reduction of Carbonyl Compounds to
Alcohols
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
Example
Example
H
+ H-OH H H
OH
H O
OH
End of Chapter