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Carbonyl Compounds

Carbonyl compounds Preparation


1. Ozonolysis
O O O3 C C ice-cold chloroform C O H2O / H + Zn dust C O O C C

Carbonyl compounds Preparation


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

Anhy. AlCl3

R C O + HCl

Carbonyl compounds Preparation


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

Normally, ketone is formed.

Carbonyl compounds Preparation


5. Decarboxylation
R (RCOO)2Ca O C R + CaCO3

Carbonyl compounds Preparation


6. From Acid Chloride (Good method)
R C Cl O + H2 H Pd / BaSO4 R C O + HCl

It is a good method to prepare aldehyde.

Carbonyl compounds Physical properties


Methanal is a gas, other lower members of aldehydes and ketones are liquids. Benzenecarbaldehyde is a colourless liquid with almond smell. Ethanal and propanone are miscible with water due to the formation of H-bond with water molecules while benzenecarbaldehyde is insoluble in water.

Carbonyl compounds Chemical properties


1. Reduction ( to alcohol)
O C R.A. OH 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 LiAlH4, also reduce acid & acid derivative)

Carbonyl compounds Chemical properties


1. Reduction (To alkane) Clemmensen Reduction / Wolff-Kishner Reduction
H O C C H

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 Fehlings solution
RCHO + Cu(OH)2 + NaOH

RCOONa

Cu2O

OH2

Carbonyl compounds Chemical properties


2. Oxidation (contd) b. With Tollens reagent / Silver mirror test
RCHO + Ag2O + NH3 Ag(NH3)2OH (Tollen's reagent)

RCOONH4 + Ag + H2O

Tollens reagent is formed from silver nitrate solution and aq. ammonia This is called silver mirror test.

Carbonyl compounds Chemical properties


2. Oxidation (contd) Oxidize aldehyde to acid
R C H O MnO4 - / H + , (or Cr2O72-/ H + , ) R C HO O

Carbonyl compounds Chemical properties


2. Oxidation (contd) Oxidize ketone to acid
O excess O.A. CH3 C CH2CH3 reflux for long time R C O 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 H3C C

I2, NaOH

I3C

I2, NaOH

CHI3 + yellow ppt.

O Na+

OH , H3C C H

This is served as a test for H3C

Carbonyl compounds Chemical properties


4. Nucleophilic Addition reaction
+ H Nu C O Nu C O OH2 Nu C OH

Energy Profile

Reaction Coordinate

Carbonyl compounds Chemical properties


4. Nucleophilic Addition reaction (contd) Reactivity:
H C H O H R C O R R C O H Ar C O Ar Ar C O

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 (contd) Factors affecting reactivity: Electronic Factor Benzenecarbaldehyde has low reactivity due to the loss of resonance energy when attacked by nucleophile.

Carbonyl compounds Chemical properties


4. Nucleophilic Addition reaction (contd) Electronic Factor
Nu C H O Nu C O H

C H

Carbonyl compounds Chemical properties


4. Nucleophilic Addition reaction (contd) Steric Factor Carbonyl carbon change from sp2 to sp3 hybridization which leads to increase in crowding. If the R group is more bulky, the intermediate will be more unstable.

Carbonyl compounds Chemical properties


4. Nucleophilic Addition reaction (contd) With HCN (or KCN / H+)
HCN + C + H2O / H

NC

OH

HOOC

OH

cyanohydrin

Carbonyl compounds Chemical properties


4. Nucleophilic Addition reaction (contd) With HCN (or KCN / H+) Mechanism +
H CN C O NC C O OH2 NC C OH

+ O +H

CN

+ O H

NC

OH

The carbonyl compound is regenerated when alkali is added to cyanohydrin.

Carbonyl compounds Chemical properties


4. Nucleophilic Addition reaction (contd) With NaHSO3 OH
O C + NaHSO3 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 (contd) With NaHSO3
O C + NaHSO3 OH C SO3Na NaOH O C

Carbonyl compounds Chemical properties


4. Nucleophilic Addition reaction (contd) With ROH (Ketal / Acetal formation) OR
O OH C ROH C R' H dry HCl R' ROH H R' dry HCl C OR acetal H

OR hemiacetal

O ROH C R' R'' dry HCl R'

OH C ROH R'' R' dry HCl

OR C OR ketal R''

OR hemiketal

Carbonyl compounds Chemical properties


4. Nucleophilic Addition reaction (contd) With ROH (Ketal / Acetal formation) Carbonyl compound is regenerated if H+ is added with water. Acetal and ketal are used as a protecting group.

Carbonyl compounds Chemical properties


4. Nucleophilic Addition reaction (contd) With ROH (Ketal / Acetal formation)
O COOC2H5 OH (not possible)
OH OH C

COO + C2H5OH

dry HCl

OH2 O O O O

COOC2H5

OH

COO + C2H5OH

Carbonyl compounds Chemical properties


5. Condensation reaction
O C + :NH2 G N C G + H2O

Carbonyl compounds Chemical properties


5. Condensation reaction (contd) O Mechanism:
C :NH2 G O C + N H H G proton shift G + H2O OH C H N G

Nucleophilic addition followed by elimination


N C

Carbonyl compounds Chemical properties


5. Condensation reaction (contd) With hydroxylamine OH
O N C :NH2 OH C oxime + H2O

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 (contd) With hydrazine
O C :NH2 NH2 N C hydrazone NH2 + H2O

hydrazine

Carbonyl compounds Chemical properties


5. Condensation reaction (contd) With phenylhydrazine
O C :NH2 N H H N C phenylhydrazone phenylhydrazine N + H2O

Carbonyl compounds Chemical properties


5. Condensation reaction (contd) With 2,4-dinitrophenylhydrazine
O2N O C :NH2 N NO2 H H N C orange ppt. NO2 N NO2 + H2O

Carbonyl compounds Chemical properties


5. Condensation reaction (contd) With 2,4-dinitrophenylhydrazine This method is used for identification of original carbonyl compound by checking the melting point of the derivatives.

Carbonyl compounds Chemical properties


5. Condensation reaction (contd) With 2,4-dinitrophenylhydrazine Criteria on choosing a suitable derivative for identification:
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 C H O C + PCl5 H C H Cl C Cl alcoholic KOH reflux C C + POCl3

Carbonyl compounds Chemical properties


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

-hydrogen

Carbonyl compounds should contain -hydrogen

H H2O + H3C C

H C

O C H

Carbonyl compounds Chemical properties


7. Aldol Condensation (contd) Mechanism:
O C H C H C O C H C C O C H O C H

-hydrogen

HO

H C C OH C

O C H OH2 C

H C O C

O C H

Carbonyl compounds Chemical properties


7. Aldol Condensation (contd) The carbonyl compounds should contain hydrogen. The -hydrogen in carbonyl compound is quite acidic since the anion (carbanion) is resonance stabilized.
O C C H C O C H

Carbonyl compounds Chemical properties


7. Aldol Condensation (contd) H Example:
H H C H H C H H C H O conc. KOH C H
H C H H C H H C OH H C O C H H C H H C H H C H H

H H C H

H C H

H C H C H C

O C H

warming

CH2CH3

Carbonyl compounds Chemical properties


Crossed aldol condensation reaction
O C H H + CH3CHO conc. NaOH OH C CH2CHO

Carbonyl compounds Chemical properties


8. Cannizaro Reaction
O C H conc. NaOH CH2OH + O C ONa

Dismutation reaction (disproportionation) Benzaldehyde (with no -H) is oxidised, and at the same time, reduced.

Carbonyl compounds Chemical properties


9. With Schiffs Reagent Only aldehyde will turn it purple.

Carbonyl compounds Uses of carbonyl compounds


Uses: 1. Methanal in the manufacture of ureamethanal resin. 2. Propanone as a solvent and a raw material in the manufacture of perspex.