Carbonyl Compounds

(Chapter 35)
 Carbonyl compounds
C O Carbonyl group

sp2 hybridized carbon

Coplanar σ bonds, 120o bond angle
p-p overlap π bond

Two types of compounds

H R’
Aldehyde C O Ketone C O
R R
 Polarity of carbonyl bond
Dipole moment
propan-1-ol 1.69D
propanone 2.88
ethanal 2.72

σ-bond -ve inductive effect

Cσ+ Oσ-
π-bond readily polarizable
(mesomeric effect)

Cσ+ Oσ- C+ O:-

 Chemical reaction

H
C O C+ O C OH
H-Br :Br- Br

No electrophilic additions (why?)

 Chemical reaction
No electrophilic additions (why?)

Energetic Factor
Big +ve,
unstable
C OH ∆H product
Br
(Unstable)
 Chemical reaction
No electrophilic additions (why?)
Big +ve Ea ,
unstable
Kinetic Factor Transition
state
C+ OH Ea

(Unstable)
 Chemical reaction

No nucleophilic substitution

C O C O-
Nu-:
Nu
 Nucleophilic Addition
H/R’ H/R’

C O R C O-
Nu -:
R Nu
H/R’
R C E+
E Reactivity:
2. Electrophilicity of C atom
CN of the C=O group.
• Strength of Nu:-
• Steric effect at the carbonyl
group
 Addition of HCN

H/R’ H/R’
C O + H-CN R C OH
R CN

Reactivity: HCHO > CH3CHO > ArCHO > CH3COCH3

> CH3COR > RCOR > ArCOAr
 Nucleophilic Addition
Addition of HCN (using KCN+H+)

H/R’ H/R’
slow
C O R C O-
CN :
- Note:
R CN HCN is NOT
H/R’ fast used.
Because
R C HCN 5. Toxic
OH
Cyanohydrin 6. Weak acid
(2-hydroxynitrile) CN little CN-
Usefulness in organic synthesis

H/R’ H/R’
H2O,H+ R C
R C OH OH
reflux
CN COOH

c.H2SO4,heat
•+1 carbon (longer carbon
-C=C-COOH chain)
(α,β-unsaturated acid) •2 functional group
 Addition of sodium
hydrogensulphate(IV)
C-S bond is formed as S is more nucleophilic than O
R’ R’
Room temp.
C O R C O-Na+
..
Na+ HSO3- R SO3H
R’
Sodium
hydrogensulphate(IV R C OH
) adduct, isolated as
colourless crystals SO3- Na+
 Addition of sodium
hydrogensulphate(IV)
•Limit to aliphatic aldehydes and sterically
unhindered ketones (steric effect)

% product from 1mol NaHSO3 in 1 hour:

CH3 CH3 C2H5
C=O =O
C=O C=O
H
89% CH3 CH3 35%
56% 36%
(CH3)2CH (CH3)3C C2H5 Ph
C=O C=O C=O C=O
CH3 CH3 C2H5 2% CH3 1%
12% 6%
 Addition of sodium
hydrogensulphate(IV)
•Reversible (can be reversed by aq. Alkali or
acid by shifting eqm. position to LHS by
HSO3- + H+=> SO2 , HSO3- + OH- => SO32-)

•Use to purify liquid or gaseous carbonyl

compounds which are difficult to purify
by direct recrystallization.
 Addition-elimination
(condensation)
R’
H H R’
C O
HO N: HO N+ C O-
R
H
H R
(Hydroxylamine)

H R’ R’
-H2O
HO N C OH HO N C
R
R (Oxime)
 Addition-elimination
R’
.. .. R’
NO2 .. .. C O NO2
NH-NH2 NH-N=C
R R

NO2 NO2
2,4-dinitrophenylhydrazine 2,4-dinitrophenylhydrazone
(Brady’s reagent) (yellow or light orange crystals)
 Phenylhydrazone
•Products have sharp and characteristic
melting point.
•Used as the identification of the original
aldehyde and ketone

Note:
• NH3 does not react
• Predict the product obtained by
adding H2N-NH2 to propanal.
 Oxidation

• KMnO4/H+ , K2Cr2O7/H+ (Strong oxidizing agent)

RCHO => RCOOH

RCH2COCH2R’ => RCOOH + R’ CH2COOH +
RCH2COOH + R’COOH
C6H5CHO => C6H5COOH requiring reflux for hours
 Oxidation
1. Tollen’s reagent (silver mirror test)

Reagent: 2Ag+ + 2OH- => Ag2O + H2O

Ag2O + 4NH3 + H2O => 2Ag(NH3)2OH

2[Ag(NH3)2]+ + RCHO + 3OH-

=> RCOO- +2H2O + 4NH3 + 2Ag (mirror)

No reaction with ketone

(Tollen’s reagent is a mild O.A.)
 Oxidation
1. Fehling’s reagent

Reagent: alkaline solution of copper(II) tartrate

RCHO + 2Cu2+ + 5OH- => RCOO- + 3H2O + Cu2O

(Fehling) (brick-red)

Note: No reaction with Ketones and Aromatic Aldehydes

 Reduction
Reducing agent: LiAlH4 Lithium Tetrahydridoaluminate
NaBH4 Sodium Tetrahydridoborate
Both equivalent to a source of hydride ion, H-.

R R O- R OH
C H+
C O C
H/R H/R H H/R H
H-
 Reduction
LiAlH4 must be kept dry
i.e. in solution of dry ether

LiBH4 is less powerful,

can be used in aqueous solution.
Reducing agent: H2/Ni, similar to alkene
R H2/Ni
C O RCH2OH
H/R
 Triiodomethane reaction
CH3 OH- CH2
-
CH2X
X2
C O C O C O
H/R -H2O -X-
H/R H/R
X2 CX3 OH- CX3
X2
C O HO C O-
-X-
-X- H/R
H/R
CX3- + R/HCOOH CHX3 + RCOO-

(RCOCH3 + I2/OH- => RCOO- + CHI3 ,yellow ppt.)