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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
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
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 CC)
2. Na/ Hg in ethanol
(also reduce RX)
3. LiAlH4, NaBH4
(for LiAlH , also reduce acid & acid derivative)
Carbonyl compounds –
Chemical properties
O C C
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
2. Oxidation (cont’d)
b. With Tollen’s reagent / Silver mirror test
RCHO + Ag2O + NH3 RCOONH4 + Ag + H2O
Ag(NH3)2OH
(Tollen's reagent)
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)
3. Iodoform reaction
O O O
I2, NaOH I2, NaOH -
H3C C I3C C CHI3 + C O Na+
yellow ppt.
O OH
H
Carbonyl compounds –
Chemical properties
Energy Profile
Reaction Coordinate
Carbonyl compounds –
Chemical properties
Nu
O O
C C
Nu H
H
O
+ C
H
Carbonyl compounds –
Chemical properties
+
H2O / H
HCN + C O NC C OH HOOC C OH
cyanohydrin
Carbonyl compounds –
Chemical properties
+ +
C O +H CN C O NC C OH
H
OH O
O
C NaOH
C + NaHSO3 C
SO3Na
Carbonyl compounds –
Chemical properties
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
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
C + H2O C
H N G
Carbonyl compounds –
Chemical properties
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
phenylhydrazone
phenylhydrazine
Carbonyl compounds –
Chemical properties
orange ppt.
NO2
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
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
C C C C
H H
Carbonyl compounds –
Chemical properties
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
8. Cannizaro Reaction
O O
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.