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OXIDATION,
REDUCTION AND SYNTHESIS
SUBTOPIC
1.
2.
3.
Naming aldehyde and ketone (or sketch the hydrocarbon given its
IUPAC name).
Physical properties of aldehyde and ketone (boiling point, solubility)
Reaction of aldehyde and ketone.
reduction of aldehyde and ketone using catalytic reduction
hydride reducing reagents: NaBH4, LiAlH4
complete removal of carbonyl group; Clemmensen and Wolf-Kishner Reduction
4.
5.
and
one p bond formed by the overlap of parallel 2p orbitals
Structure of Aldehydes
The functional group of an aldehyde is a carbonyl
carbon atom
H
C
H
Methanal
(formaldehyde)
H3 C
Ethanal
(acetaldehyde)
Structure of Ketones
The functional group of a ketone is a carbonyl
O
3
Cyclohexanone
NOMENCLATURE
ALDEHYDE AND KETONE
1. Name by the IUPAC system on aldehyde and ketone
structure (or sketch the hydrocarbon given its IUPAC
name).
PAGE : 730-731
Chapter 2
Nomenclature-Aldehydes
IUPAC names: select as the parent alkane the
the C=C by changing the infix -an- to -en the location of the suffix determines the numbering
pattern
Nomenclature-Aldehydes
O
CH3CH
O
CH3CH2CH
CH3
CH3CHCH2CH2CHCH
CH2CH3
ethanal
propanal
2-ethyl-5-methylhexanal
Nomenclature-Aldehdyes
For cyclic molecules in which the -CHO group is
2-cyclopentenecarbaldehyde
Nomenclature-Ketones
IUPAC names:
select as the parent alkane the longest chain that contains the
carbonyl group,
indicate its presence by changing the suffix -e to -one, and
number to give C=O the smaller number
O
CH3CH2CCH2CH2CH2
3-hexanone
O
CH3CH
CHCH2CCH3
4-hexen-2-one
CH3CH2CCH2CCH3
2,4-hexanedione
Sometimes, acyl groups must be named as substituents. The three most common
acyl groups are shown below
Chapter 2
11
Chapter 2
12
BOILING POINTS
O
CH3 C CH3
CH3CH2CH2-OH
1-propanol
methoxyethane
propanal
acetone
bp 8oC
bp 49oC
bp 56 C
bp 97oC
WATER SOLUBILITIES
- ketones and aldehydes have lone pairs of electrons
and can act as hydogen bond acceptors with other
compounds having O-H or N-H bonds.
- for example, the OH hydrogen of water or an alcohol
can form a hydrogen bond with unshared electrons on
a carbonyl oxygen atom.
R
+ -
C O
C O
R'
+ -
hydrogen bonding
H
O
hydrogen bonding
R
O
-
Chapter 2
17
Mechanism of Reduction
18
Reduction
Aldehydes can be reduced to 1 alcohols and ketones
Aldehydes
O
Can be
Reduced to
Ketones
Can be
Reduced to
OH
RCH 2 OH
RCH
RCHR'
RCR'
RCH 3
RCH 2 R'
gives an alcohol
Note that organic reduction reactions add the equivalent
of H2 to a molecule
Chapter 2
20
Chapter 2
21
OH
+
H2
Pt
25o C, 2 atm
Cyclohexanone
Cyclohexanol
conditions
O
H
CH
C
H3 C
H
trans-2-Butenal
(Crotonaldehyde)
2 H2
Ni
CH 3 CH 2 CH 2 CH 2 OH
1-Butanol
powerful nucleophile
H
H
S odium
borohydride
Li + H-Al-H
H
Lithium aluminum
hydride (LAH)
Na H-B-H
H
H
Hydride ion
Chapter 2
24
NaBH4 Reduction
The key step in metal hydride reduction is transfer of
+
Na H-B-H + R-C-R'
O BH 3 Na
R-C-R'
H
from the hydride
reducing agent
H2 O
OH
R-C-R'
H
from
water
O
RCH=CHCR'
1 . NaBH 4
2. H 2O
O
RCH=CHCR'
+ H2
Rh
OH
RCH=CHCHR'
O
RCH 2 CH 2 CR'
Chapter 2
27
(R 2 CHO) 4 Al Li
A tetraalky aluminate
H2 O
OH
4 RCHR + aluminum salts
base.
Chapter 2
29
O
C
CH2CH3
Zn(Hg)
CH2CH2CH3
HCl, H2O
O
CH2
Zn(Hg)
H
CH2
CH3
HCl, H2O
Chapter 2
30
O
CCH 3 + H2 NNH 2
Hydrazine
KOH
diethylene glycol
(reflux)
CH 2 CH 3 + N2
Chapter 2
+ H2 O
31
Wolff-Kishner Reduction
O
R
N
R
NH2
OH
N
H2O
R
N H
N
R
N H
R
H2O
H
R
R
H2O
H
H2O N N R
R
N
H
R
N H
R H
OH
PREPARATION OF ALDEHYDE
4. Predict the product of aldehydes and ketones from
reduction of acid chlorides and esters using
Rosenmund Reduction and DIBAL-H
Chapter 2
33
PCC
CH2Cl2
CHO
PCC Reagents
- Pyridinium chlorochromate is a reddish orange solid reagent
used to oxidize primary alcohols to aldehydes and secondary
alcohols to ketones.
- A reagent which stops the oxidation at the aldehyde stage is
pyridinium chlorochromate (PCC)
-PCC is made from chromium trioxide under acidic conditions
-It is used in organic solvents such as methylene chloride (CH2Cl2
Chapter 2
35
i) Reduction of an ester
O
CH3(CH2)10COCH3
O
CH3(CH2)10CH
H
DIBAH =
(CH3)2CHCH2 Al
CH2CH(CH3)2
: O:
: O:
R
..
Cl
.. :
R
1 DIBAH
+
2 H3O
aldehyde
acid
chloride
: O:
R
..
Cl
.. :
-78C
1equiv.
: O:
R
: O:
ester
R
..
OR
..
1 DIBAH
+
2 H3O
Chapter 2
aldehyde
Only 1 equivalent of
very cold DIBAL-H
is used to avoid
further reduction of
the aldehyde to an
alcohol.
38
Chapter 2
39
3) ROSENMUND REDUCTION
Chemical reaction that reduces an acid halide to
an aldehyde using hydrogen gas over palladium-oncarbon poisoned with barium sulfate.
PREPARATION OF KETONE
Chapter 2
41
Can be using;
i) PCC in CH2CI2
(CH3)3C
OH
PCC
CH2Cl2
(CH3)3C
43
O
CH3 (CH2)4 C
+
Cl
hexanoyl chloride
O
CH3 (CH2)4 C
2-heptanone
CH3
- 78C
ether
Chapter 2
45
+
NH3)2
_
+
3 OH
O
H2O
2 Ag + R C O
Chapter 2
_
+
4 NH3 +
2 H2O
46
4 N
Tollen's test
Ag2O
H
OH
O
propanoic acid
propanal
ketone
no reaction
Fehling's test
H3C
O
ethanal
ketone
2CuO
H3C
OH
+
Chapter
2
no reaction
47