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Carbonyl Compounds

Carbonyl compounds –
Preparation

1. Ozonolysis
O O
O3
C C C C
ice-cold
O
chloroform

H2O / H +
Zn dust

C O O C
Carbonyl compounds –
Preparation

2. Oxidation of alcohol
H
MnO4- / H + R
R C OH C O

If primary alcohol is oxidized, distill out the aldehyde


immediately. But normally aldehyde is difficult to
synthesize.
Carbonyl compounds –
Preparation

3. Acylation of benzene

R
R Anhy. AlCl3
C O
+ C O
+ HCl
Cl
Carbonyl compounds –
Preparation

4. Hydration of Alkyne
H OH
dil. H2SO4
C C + H2O C C
HgSO4
Tautomerisation
H O

C C

H
Normally, ketone is formed.
Carbonyl compounds –
Preparation

5. Decarboxylation

R
(RCOO)2Ca O C + CaCO3
R
Carbonyl compounds –
Preparation

6. From Acid Chloride (Good method)


R R
Pd / BaSO4
C O + H2 C O + HCl
Cl H

It is a good method to prepare aldehyde.


Carbonyl compounds –
Physical properties

 Methanal is a gas, other lower members of ald


ehydes and ketones are liquids.
 Benzenecarbaldehyde is a colourless liquid wit
h almond smell.
 Ethanal and propanone are miscible with water
due to the formation of H-bond with water mol
ecules while benzenecarbaldehyde is insoluble
in water.
Carbonyl compounds –
Chemical properties

1. Reduction ( to alcohol) OH
R.A.
O C C

H
R.A.: 1. Can be H2 / Pt, Ni or Pd
(also reduce C=C and CC)
2. Na/ Hg in ethanol
(also reduce RX)
3. LiAlH4, NaBH4
(for LiAlH , also reduce acid & acid derivative)
Carbonyl compounds –
Chemical properties

1. Reduction (To alkane)


Clemmensen Reduction / Wolff-Kishner Reduct
ion
H

O C C

a. Clemmensen reduction: Zn / Hg in conc.HCl


b. Wolff-Kishner reduction: NH2NH2 in NaOH
Carbonyl compounds –
Chemical properties

2. Oxidation
Special oxidation of aldehyde
Serve as a test to distinguish aldehyde from
ketone. (These are very important tests)
a. With Fehling’s solution

RCHO + Cu(OH)2 + NaOH RCOONa + Cu2O + OH2


Carbonyl compounds –
Chemical properties

2. Oxidation (cont’d)
b. With Tollen’s reagent / Silver mirror test
RCHO + Ag2O + NH3 RCOONH4 + Ag + H2O

Ag(NH3)2OH
(Tollen's reagent)

Tollen’s reagent is formed from silver nitrate solution


and aq. ammonia
This is called silver mirror test.
Carbonyl compounds –
Chemical properties

2. Oxidation (cont’d)
Oxidize aldehyde to acid
R MnO4 - / H + , R
C O C O
H (or Cr2O72-/ H + , ) HO
Carbonyl compounds –
Chemical properties

2. Oxidation (cont’d)
Oxidize ketone to acid
O R
excess O.A.
CH3 C CH2CH3 C O
reflux for long time
HO
(bond breaking)

This reaction is not good method because you


cannot control where the bond break.
Carbonyl compounds –
Chemical properties

3. Iodoform reaction
O O O
I2, NaOH I2, NaOH -
H3C C I3C C CHI3 + C O Na+
yellow ppt.

O OH

This is served as a test for H3C C , H3C C

H
Carbonyl compounds –
Chemical properties

4. Nucleophilic Addition reaction


+
H OH2
Nu C O Nu C O Nu C OH

Energy Profile

Reaction Coordinate
Carbonyl compounds –
Chemical properties

4. Nucleophilic Addition reaction (cont’d)


Reactivity:
H R R Ar Ar
C O C O C O C O C O
H H R H Ar

Factors affecting reactivity:


Electronic Factor
Positive inductive effect of alkyl group make the carbonyl
carbon to be less positive.
Carbonyl compounds –
Chemical properties

4. Nucleophilic Addition reaction (cont’d)


Factors affecting reactivity:
Electronic Factor
Benzenecarbaldehyde has low reactivity due to th
e loss of resonance energy when attacked by nucl
eophile.
Carbonyl compounds –
Chemical properties

4. Nucleophilic Addition reaction (cont’d)


Electronic Factor

Nu
O O
C C
Nu H
H

O
+ C

H
Carbonyl compounds –
Chemical properties

4. Nucleophilic Addition reaction (cont’d)


Steric Factor
Carbonyl carbon change from sp2 to sp3 hybridizati
on which leads to increase in crowding. If the R gr
oup is more bulky, the intermediate will be more un
stable.
Carbonyl compounds –
Chemical properties

4. Nucleophilic Addition reaction (cont’d)


With HCN (or KCN / H+)

+
H2O / H
HCN + C O NC C OH HOOC C OH

cyanohydrin
Carbonyl compounds –
Chemical properties

4. Nucleophilic Addition reaction (cont’d)


With HCN (or KCN / H+)
Mechanism +
H OH2
CN C O NC C O NC C OH

+ +
C O +H CN C O NC C OH
H

The carbonyl compound is regenerated when alkali


is added to cyanohydrin.
Carbonyl compounds –
Chemical properties

4. Nucleophilic Addition reaction (cont’d)


With NaHSO3 OH
O
+ NaHSO3 C
C
SO3Na

On cooling, the bisulphite addition compound is crystallized.


This reaction is a method for purification and separation
of carbonyl compound (also identification). The carbonyl
compound is regenerated by addition of alkali.
Carbonyl compounds –
Chemical properties

4. Nucleophilic Addition reaction (cont’d)


With NaHSO3

OH O
O
C NaOH
C + NaHSO3 C
SO3Na
Carbonyl compounds –
Chemical properties

4. Nucleophilic Addition reaction (cont’d)


With ROH (Ketal / Acetal formation) OR
OH
O
ROH ROH C
C R' H
C R' H
dry HCl dry HCl
R' H OR OR
hemiacetal acetal

OH OR
O
ROH ROH C
C R' R''
C R' R''
dry HCl dry HCl
R' R'' OR OR
hemiketal ketal
Carbonyl compounds –
Chemical properties

4. Nucleophilic Addition reaction (cont’d)


With ROH (Ketal / Acetal formation)
Carbonyl compound is regenerated if H+ is ad
ded with water.
Acetal and ketal are used as a protecting gro
up.
Carbonyl compounds –
Chemical properties

4. Nucleophilic Addition reaction (cont’d)


With ROH (Ketal / Acetal formation)
O COOC2H5 O COO
OH
+ C2H5OH
(not possible)
OH OH

dry HCl C C
OH2

O O
COOC2H5 OH COO
O O + C2H5OH
Carbonyl compounds –
Chemical properties

5. Condensation reaction
G
O N

C + :NH2 G C + H2O
Carbonyl compounds –
Chemical properties

5. Condensation reaction (cont’d) -


O
Mechanism: O
:NH2 G C
C
+
H N H
G
Nucleophilic addition
proton shift
followed by elimination
G OH
N

C + H2O C

H N G
Carbonyl compounds –
Chemical properties

5. Condensation reaction (cont’d)


With hydroxylamine OH
O N
C :NH2 OH C + H2O

oxime
From aldehyde, product is aldoxime
From ketone, product is ketoxime
They are white solids.
The reaction can thus serve as a test for carbonyl
compounds.
Carbonyl compounds –
Chemical properties

5. Condensation reaction (cont’d)


With hydrazine
NH2
O N
C :NH2 NH2 C + H2O
hydrazine
hydrazone
Carbonyl compounds –
Chemical properties

5. Condensation reaction (cont’d)


With phenylhydrazine
H
O H N
C :NH2 N N
+ H2O
C

phenylhydrazone
phenylhydrazine
Carbonyl compounds –
Chemical properties

5. Condensation reaction (cont’d)


With 2,4-dinitrophenylhydrazine
O2N
H
O H N NO2
C :NH2 N N
NO2 + H2O
C

orange ppt.
NO2
Carbonyl compounds –
Chemical properties

5. Condensation reaction (cont’d)


With 2,4-dinitrophenylhydrazine

This method is used for identification of origin


al carbonyl compound by checking the melting
point of the derivatives.
Carbonyl compounds –
Chemical properties

5. Condensation reaction (cont’d)


With 2,4-dinitrophenylhydrazine
Criteria on choosing a suitable derivative for id
entification:
1. Little side product
2. Reaction should be easily carried out
3. Derivatives should be easily purified.
4. The difference in melting point between the derivatives
of consecutive members is large.
Carbonyl compounds –
Chemical properties

6. With PCl5
H O H Cl

C C + PCl5 C C + POCl3

H H Cl

alcoholic KOH
reflux

C C
Carbonyl compounds –
Chemical properties

7. Aldol Condensation
H O H O H H O
conc. KOH
H C C H C C H3C C C C
H H H
H H OH H
-hydrogen
warming

H H O
Carbonyl compounds
should contain -hydrogen H2O + H3C C C C
H
Carbonyl compounds –
Chemical properties

7. Aldol Condensation (cont’d)


Mechanism:
O O O

C C C C C C
H H H
H O

-hydrogen HO
C C
H

H O H O
OH2
C C C C C C C C
H H
OH O
Carbonyl compounds –
Chemical properties

7. Aldol Condensation (cont’d)


The carbonyl compounds should contain -hyd
rogen.
The -hydrogen in carbonyl compound is quite
acidic since the anion (carbanion) is resonance
stabilized.
O O

C C C C
H H
Carbonyl compounds –
Chemical properties

7. Aldol Condensation (cont’d)


Example: H H H O

H C C C C
H H H O
conc. KOH H
H H
H C C C C H H H

H H C C C C H
H H H
OH H H H

H H H O warming

H C C C C C C
H
H H H H CH2CH3
Carbonyl compounds –
Chemical properties

Crossed aldol condensation reaction


O OH
conc. NaOH
C + CH3CHO C CH2CHO
H
H
Carbonyl compounds –
Chemical properties

8. Cannizaro Reaction
O O

C conc. NaOH CH2OH C


H ONa
+

Dismutation reaction (disproportionation)


Benzaldehyde (with no -H) is oxidised, and at the
same time, reduced.
Carbonyl compounds –
Chemical properties

9. With Schiff’s Reagent


Only aldehyde will turn it purple.
Carbonyl compounds –
Uses of carbonyl compounds

Uses:
1. Methanal in the manufacture of urea-methana
l resin.
2. Propanone as a solvent and a raw material in
the manufacture of perspex.

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