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Structure of Aldehydes
The functional group of an aldehyde is a
carbonyl group bonded to a H atom
in methanal, it is bonded to two H atoms
in all other aldehydes it is bonded to one H and
one carbon atom
H
H
C
H
M e t ha na l
( fo rm a lde hy de )
H3 C
E tha na l
( a c e t a lde hyde )
Structure of Ketones
The functional group of a ketone is a
carbonyl group bonded to two carbon atoms
O
CH3 -C-CH3
Propanone
(Acetone)
Cyclohexanone
Nomenclature-Aldehydes
IUPAC names: select as the parent alkane the
longest chain of carbon atoms that contains the
carbonyl group
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 attached to the ring, the name is
derived by adding the suffix -carbaldehyde
to the name of the ring
O
C
H cyclohexanecarbaldehyde C
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
Nomenclature-Ketones
The IUPAC system retains the names
acetone, acetophenone, and benzophenone
O
C H3 C C H3
A c e to ne
C C H3
C-
A c e to phe no ne
B e nzo phe no ne
Physical Properties
Oxygen is more electronegative than carbon (3.5
vs 2.5) and, therefore, a C=O group is polar
aldehydes and ketones are polar compounds and interact
in the pure state by dipole-dipole interaction
they have higher boiling points and are more soluble in
water than nonpolar compounds of comparable molecular
weight
+ C
O
Preparation of Aldehydes
Primary Alcohols are oxidized to aldehydes.
CH2OH
PCC
CH2Cl2
CHO
Preparation of Aldehydes
Alkenes with a vinylic hydrogen undergo oxidative cleavage
when treated with ozone to yield aldehydes.
On cyclic alkenes a dicarbonyl compound is formed
1. O3
2. Zn, CH3COOH
CH3CCH2CH2CH2CH2CH
Preparation of Aldehydes
O
CH3(CH2)10COCH3
O
CH3(CH2)10CH
H
DIBAH =
(CH3)2CHCH2 Al
CH2CH(CH3)2
Preparation of Ketones
Secondary alcohols are oxidized to give ketones.
(CH3)3C
OH
PCC
CH2Cl2
(CH3)3C
Preparation of Ketones
Ozonolysis of alkenes yields ketones if one of the
unsaturated carbon atoms is disubstituted.
CH2
CH3
1. O3
2. Zn, CH3COOH
O
CH3
+ CH2O
Preparation of Ketones
Aryl ketones are prepared by Friedel-Crafts
acylation of an aromatic ring with an acid chloride
in the presence of AlCl3 catalyst.
O
O
CH3CCl
AlCl3
HEAT
CH3
Preparation of Ketones
Methyl ketones are prepared by hydration of
terminal alkynes in the presence of Hg2+ catalyst.
CH3(CH2)3C CH
H3O+
HgSO4
O
CH3(CH2)3C CH3
REACTIONS OF ALDEHYDES
AND KETONES
Reaction Themes
One of the most common reaction themes
of a carbonyl group is addition of a
nucleophile to form a tetrahedral carbonyl
addition compound
O
R
Nu
C
R
Nu
C
R
R
Tetrahedral carbonyl
addition compound
Reaction Themes
A second common theme is reaction with a
proton or Lewis acid to form a resonancestabilized cation
R
R
+ H-B
fast
R
C
R
+
O H
+ B
Nucleophiles
Nucleophiles can be negatively charged ( : Nu) or neutral ( :
Nu) at the reaction site
The overall charge on the nucleophilic species is not
considered
Relative Reactivity
O
RCH(OH)C N
O
C
HO
H
HCN
CN
C
O
C
O
H
C N
HO
CN
C
HCN
CN
C
C N
OH
OH
H
HCN
CHCN
1. LiAlH4, THF
2. H2O
CHCH2NH2
OH
+
H3O , heat
CHCOOH
Addition of Alcohols
A ketone or aldehyde reacts reversibly with two
equivalents of an alcohol in the presence of an acid
catalyst to yield an acetal, R2C(OR)2.
O
R
OR
2ROH
R
R
R
OR
H2O
Addition of Alcohols
Acidic conditions cause protonation of the
carbonyl group.
Reactivity is increased.
O
C
H A
O
C
Addition of Alcohols
H Cl
ROH
O
C
H
O
R
OH2
OH2
C
H Cl
OR
ROH
O
C
H3O+
OR
hemiacetal
R
O
O
C
R
OH2
R
O
acetal
Addition of Alcohols
Addition of one molecule of alcohol to the
C=O group of an aldehyde or ketone gives a
hemiacetal
Hemiacetal: a molecule containing an -OH
and an -OR or -OAr bonded to the same
carbon
O
OH
CH3 COCH2 CH3
CH3
A hemiacetal
Addition of Alcohols
Hemiacetals are only minor components of
an equilibrium mixture, except where a
five- or six-membered ring can form
(the trans isomer is shown here)
O
CH3 CHCH2 CH2 CH
OH
4-Hydroxypentanal
H3 C
OH
A cyclic hemiacetal
(major form present
at equilibrium)
Addition of Alcohols
Formation of a hemiacetal is acid-catalyzed
Step 1: proton transfer from the acid, HA, to
the carbonyl oxygen
CH3 -C-CH3 + A -
+
O-H
Addition of Alcohols
Step 2: attack of ROH on the carbonyl carbon
followed by proton transfer to A- to
regenerate the acid catalyst
+
O-H
O-H
O-H
CH3 -C-CH3
+
O
- H R
A
Addition of Alcohols
Hemiacetals react with alcohols to form
acetals
Acetal: a molecule containing two -OR or
-OAr groups bonded to the same carbon
OH
CH3 COCH2 CH3 + CH3 CH2 OH
CH3
A hemiacetal
OCH2 CH3
CH3 COCH2 CH3
CH3
A diethyl acetal
H2 O
OXIDATION OF ORGANIC
COMPOUNDS
O
R
[O]
H
O
R
[O]
R
OH
no reaction
O
CH3(CH2)4CH
CrO3, H3O
acetone
O
CH3(CH2)4COH
O
H
Ag2O
NH4OH, H2O,
EtOH
O
OH
OH
O
R
C
H
OH
CrO3
H3O+
OH
1. KMnO4, H2O,
NaOH
+
2. H3O
COOH
COOH
REDUCTION OF CARBONYL
COMPOUNDS
Reduction
Aldehydes can be reduced to 1 alcohols
and ketones to 2 alcohols. In addition, the
C=O group can be reduced to a -CH2- group
Aldehydes
O
RCH
Can be
Reduced to
RCH2 OH
RCH3
Ketones
O
RCR'
Can be
Reduced to
OH
RCHR'
RCH2 R'
Catalytic Reduction
Catalytic reductions are generally carried
out from 25 to 100C and from 1 to 5 atm
H2
O
OH
+ H2
Cyclohexanone
Pt
25oC, 2 atm
Cyclohexanol
Catalytic Reduction
A carbon-carbon double bond may also be
reduced under these conditions
O
H
CH
2H2
C C
Ni
H3 C
H
trans-2-Butenal
(Crotonaldehyde)
Li+ H-Al-H
H
Lithium aluminum
hydride (LAH)
Na H-B-H
Hydride ion
NaBH4 Reduction
Reductions with NaBH4 are most commonly
carried out in aqueous methanol, in pure
methanol, or in ethanol
One mol of NaBH4 reduces four mol of
aldehyde or ketone
O
4RCH + NaBH4
methanol
+ H2 O
(RCH2 O)4 B Na
-
A tetraalkyl borate
4RCH2 OH + borate
salts
NaBH4 Reduction
The key step in metal hydride reduction is
transfer of a hydride ion to the C=O group
to form a tetrahedral carbonyl addition
compound
H
+
Na H-B-H + R-C-R'
O BH3 Na
R-C-R'
H
H2 O
OH
R-C-R'
H
from
water
LiAlH4 Reduction
Unlike NaBH4, LiAlH4 reacts violently with
water, methanol, and other protic solvents.
Reductions using it are carried out in
diethyl ether or tetrahydrofuran (THF)
O
ether
4RCR + LiAlH4
-
(R 2 CHO)4 Al Li
A tetraalky aluminate
H2 O
OH
4RCHR + aluminum salts
1. NaBH4
2. H 2 O
O
RCH=CHCR' + H2
Rh
OH
RCH=CHCHR'
O
RCH2 CH2 CR'
Clemmensen Reduction
Refluxing an aldehyde or ketone with
amalgamated zinc in concentrated HCl
converts the carbonyl group to a methylene
group
OH
O
C(CH 2 ) 5 CH3
Z n(Hg), HCl
OH
Wolff-Kishner Reduction
In the original procedure, the aldehyde or
ketone and hydrazine are refluxed with
KOH in a high-boiling solvent. The same
reaction can be brought about using
hydrazine and potassium tert-butoxide in
DMSO
O
CCH3 + H2 NNH2
KOH
diethylene glycol
Hydrazine
(reflux)
CH2 CH3 + N2
+ H2 O
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
C
R H
OH
Wittig Reaction
The Wittig reaction is a very versatile
synthetic method for the synthesis of
alkenes from aldehydes and ketones.
+ P h 3 P -C H 2
A pho s pho nium
y lide
C H2
M e t hy le ne c y c lo he x a ne
+
+ P h P -O
3
T riphe ny lpho s phine o x ide
Wittig Reaction
CH3
1. CH3MgBr
2. POCl3
CH2
_
(C6H5)3P+ CH2THF
CH2
Wittig Reaction
CH3CH2C=O
CH2CH3
+_
CHCH3
(C6H5)3P
THF
CH3CH2C=CHCH3
CH2CH3
Wittig Reaction
Examples:
O
CH3
Addn of N Nucleophiles
Ammonia, 1 aliphatic amines, and 1
aromatic amines react with the C=O group
of aldehydes and ketones to give imines
(Schiff bases)
O
CH3 CH + H2 N
CH3 CH=N
Aniline
Ethanal
+ H2 O
An imine
(A Schiff base)
+
O
Cyclopentanone
+ H2 NCH3
Methylamine
NCH3
An imine
(a Schiff base)
+ H2 O
Addn of N Nucleophiles
Formation of an imine occurs in two steps
+ H2 N-R
C N-R
C N-R
H
H
A tetrahedral carbonyl
addition compound
Addn of N Nucleophiles
Step 2: protonation of the -OH followed by loss
of H2O and proton transfer to solvent
H
O
An imine
+ H2O
Addn of N Nucleophiles
A value of imines is that the carbonnitrogen double bond can be reduced to a
carbon-nitrogen single bond
Cyclohexanone
H2 N
H+
-H2 O
Cyclohexylamine
N
(An imine)
H2 /Ni
H
N
Dicyclohexylamine
Addn of N Nucleophiles
Secondary amines react with the C=O
group of aldehydes and ketones to form
enamines
+
O + H-N
Piperidine
(a secondary amine)
N
An enamine
+ H2 O
Addn of N Nucleophiles
The carbonyl group of aldehydes and
ketones reacts with hydrazine and its
derivatives in a manner similar to its
reactions with 1 amines
O + H2 NNH2
Hydrazine
NNH2
A hydrazone
Hydrazine
H2 N-OHderivatives include
H2 N-NH
Phenylhydrazine
Hydroxylamine
+ H2 O
Acidity of -Hydrogens
Hydrogens alpha to a
carbonyl group are more
acidic than hydrogens
of alkanes, alkenes, and
alkynes but less acidic
than the hydroxyl
hydrogen of alcohols
Type of Bond
pKa
CH3 CH2 O-H 16
O
CH3 CCH2 -H
20
CH3 C C-H
25
44
51
CH2 =CH-H
CH3 CH2 -H
Acidity of -Hydrogens
-Hydrogens are more acidic because of
1. the electron-withdrawing inductive effect of
the adjacent carbonyl group weakens the C-H
bond and
2. delocalization of the negative charge stabilizes
the resulting enolate anion
O
CH3 -C-CH 2 -H +
AO
CH3 -C-CH 2
OCH3 -C=CH2
+ H-A
Keto-Enol Tautomerism
Protonation of the enolate anion on oxygen
gives the enol form; protonation on carbon
gives the keto form
O-
CH3 -C-CH2
CH3 -C=CH2
Enolate anion
H-A
A - + CH3 -C-CH3
Keto form
H-A
OH
CH3 -C=CH2 + A
Enol form
Keto-Enol Tautomerism
Acid-catalyzed equilibration of keto and
enol tautomers occurs in two steps
Step 1: proton transfer to the carbonyl oxygen
+
H
O
O
fast
CH3 -C-CH3 + H-A
CH3 -C-CH3 + A keto form
Keto-Enol Tautomerism
Step 2: proton transfer to A- to give the enol
+
CH3 -C-CH2 -H + A
slow
OH
CH3 -C=CH2 + H-A
Enol form
-Halogenation
-Halogenation: aldehydes and ketones
with at least one -hydrogen react at an
-carbon with Br2 and Cl2
O
CCH3 + Br 2
Acetophenone
CH3 CO2 H
O
CCH2 Br + HBr
-Halogenation
Acid-catalyzed -halogenation
Step 1: acid-catalyzed enolization
OH
H-O
slow
R'-C-C-R
C
R
C
R'
C
R'
C
R
Br-Br
fast
R
halogen
Br
H-O
O
C
R'
C R
R
+ H-Br
-Halogenation
Base-promoted -halogenation
slow
+ H2 O
C C
R'-C-C-R +
OH
R'
R
R
Resonance-stabilized
enolate anion
-Halogenation
Base-promoted -halogenation (contd.)
Step 2: nucleophilic attack of the enolate anion
on halogen
C
R'
O Br
Br-Br
fast
R'-C-C-R + Br
R
Haloform Reaction
In the presence of base, a methyl ketone
reacts with three equivalents of halogen to
form a 1,1,1-trihaloketone, which then
reacts with an additional mol of hydroxide
ion to form a carboxylic salt and a
trihalomethane
O
RCCH3
3Br 2
3NaOH
O
RCCBr 3
O
NaOH
RCO Na
+ CHBr3
Tribromomethane
(Bromoform)
Haloform Reaction
The final stage is divided into two steps
Step 1: addition of OH- to the carbonyl group to
form a tetrahedral carbonyl addition
intermediate, followed by its collapse
O
RC-CBr 3 + OH
O
RC-CBr 3
OH
O
RC
OH
CBr 3
Haloform Reaction
Step 2: proton transfer from the carbonyl group
to the haloform anion
O
RC-O-H +
O
CBr 3
RC-O
+ H-CBr 3
Bromoform
Ag2O
OH
O
propanoic acid
propanal
ketone
no reaction
Fehling's test
H3C
O
ethanal
ketone
2CuO
H3C
OH
O
no reaction